Method for producing battery active material and product thereof

Abstract

The present disclosure relates to the preparation of active materials useful in battery anodes and compositions thereof. The active material may be composed of natural graphite or graphitizable primary particles that are agglomerated into secondary particles with an agglomeration solution. The resulting secondary particles may be carbonized and graphitized prior to their use as battery active materials.

Description

[0001] Incorporation by reference into any priority application

[0002] This application claims the benefit of priority to U.S. Provisional Application No. 63 / 373,015 filed on August 19, 2022, U.S. Provisional Application No. 63 / 489,367 filed on March 9, 2023, and U.S. Provisional Application No. 63 / 504,982 filed on May 30, 2023, the entire disclosures of which are incorporated herein by reference in their entirety. Technical Field

[0003] Embodiments of the present application relate to an anode material comprising graphite and hard carbon and a method for preparing the same. Background Art

[0004] Graphite can be applied to a variety of different technologies, including steelmaking, lubrication, carbon reinforced plastics and batteries. Graphite is particularly useful as an anode material for various batteries, including lithium-ion batteries, because it has a two-dimensional carbon layer that allows lithium ions to be intercalated to charge and discharge the battery. Graphite has an excellent ability to limit expansion upon lithiation or lithium intercalation, which results in reduced damage to the battery. This is a significant advantage in producing batteries that are sustainable and reusable for extended charge and discharge cycles.

[0005] Natural graphite can be obtained from natural sources and deposits. Natural graphite is formed over millions of years under intense heat and pressure. On the other hand, synthetic graphite can be synthesized as a byproduct of various chemical processes. For example, synthetic graphite can be synthesized from petroleum, coal, or other synthetic or natural carbon materials. One such material that can be used to produce synthetic graphite is petroleum coke powder, which is the final byproduct of the oil refining process or the coking process. Petroleum coke is the solid, non-melting carbon left after coking, where heavy oils are cross-linked and evaporated from the feed oil.

[0006] As discussed above, graphite has carbon layers, each a single atomic layer thick, which are composed of sp 2 Aromatic rings of hybridized carbon. Graphene is simply a single graphitic carbon layer isolated from a graphite source. Graphite is useful in battery materials because it is particularly conductive and efficiently facilitates charging and discharging without causing additional side reactions or other damage to the battery.

[0007] Synthetic graphite is ideal for lithium-ion batteries due to its purity, performance, and consistency. As an anode material, synthetic graphite enables better cycle stability, faster charging, higher quality consistency, and rapid production scalability. However, traditional methods of producing anode active materials using synthetic graphite are not environmentally friendly. For example, various hazardous chemicals have been used in the process of making artificial graphite active materials and their particles. Some of the chemicals that have been used are asphalt pitch, pitch coke, coal tar, fluoranthene, pyrene, Phenanthrene, anthracene, naphthalene, fluorine, biphenyl or acenaphthene. These chemicals can be hazardous to produce and use, and they may present additional environmental hazards or environmental considerations when the battery is recycled at the end of its useful life.

[0008] Specialized equipment is also required to produce synthetic graphite anode materials, and many traditional methods for preparing synthetic graphite have used oxidative pre-treatment of the graphite precursor, which results in additional environmental hazards, energy, and cost.

[0009]

[0006] Therefore, there is a need to produce graphite materials or battery active materials comprising graphite by environmentally friendly methods that are cost-effective, more efficient than previous methods, and do not require additional specialized equipment or processing. Summary of the invention

[0010] Embodiments of the present invention can agglomerate or granulate artificial carbon powder via agglomeration solutions. In various embodiments, the agglomeration solutions are environmentally friendly, cost-effective, and can result in electrochemically stable anode materials. Using organic molecules, such as lignin, sugars, or plant-derived carbohydrates, in the agglomeration solution, primary particles can be processed to adhere to each other to maintain secondary particle structures, and the secondary particle structures can be produced on readily available equipment. Due to the improvements disclosed herein, high-quality synthetic graphite can be produced in a cost-effective manner and introduced into batteries optimized for electric vehicles, energy storage infrastructure, personal electronic devices, and many other devices.

[0011] Agglomeration of primary particles to form secondary particles and ultimately graphitized anode materials brings many benefits. One reason to agglomerate graphite in battery anodes is that this allows for more efficient storage of lithium, sodium or other ions, which can improve the overall capacity and energy density of the battery. Agglomerating graphite in battery anodes can improve the performance and manufacturability of the batteries, making them more suitable for a wide range of applications.

[0012] For the purpose of summarizing the advantages achieved compared to the prior art, certain objects and advantages of the present disclosure are described herein. In any particular embodiment of the present invention, not all of these objects or advantages can be achieved. Thus, for example, those skilled in the art will recognize that the present invention can be implemented or performed in a manner that achieves or optimizes an advantage or a group of advantages as taught herein without having to achieve other objects or advantages as taught or suggested herein.

[0013] Various embodiments disclosed herein relate to methods for producing battery anode active materials or electrochemically active materials. In various embodiments, the battery active material may include synthetic soft carbon sprayed or coated with agglomerated solutions containing organic molecules (e.g., lignin, sugars, or plant-derived carbohydrates). Agglomerated particles may be referred to as secondary particles, which are carbonized and graphitized for use as anode materials in lithium ion batteries or sodium ion batteries. Lithium ion batteries may be lithium cobalt oxide (LiCoO2 or LCO) batteries, lithium manganese oxide (LiMn2O4 or LMO) batteries, lithium iron phosphate (LiFePO4 or LFP) batteries or variants of lithium iron phosphate, lithium nickel manganese cobalt oxide (LiNiMnCoO2 or NMC) batteries, lithium nickel cobalt aluminum oxide (LiNiCoAlO2 or NCA) batteries, or lithium titanate (Li4Ti5O12 or LTO) batteries.

[0014] Method and product disclosed herein allow to produce carbon friendly, cost-effective and battery active materials that require minimum pre-granulation step and post-granulation step. The use of solution of lignin or plant-derived carbohydrate allows secondary particles or battery active materials to agglomerate in a cost-effective manner, because lignin or plant-derived carbohydrate is widely available, and lignin and carbohydrate are one of the most common organic substances on the earth except cellulose and hemicellulose (which can also be used as organic molecules in this article). Lignin and plant-derived carbohydrate are also easy to source and do not produce toxic or environmentally harmful by-products. Disclosed embodiments prevent the use of coal tar pitch or other harmful binders as agglomeration products, which reduces the environmentally unfriendly impact of producing anode active materials.

[0015] In some aspects, the technology described herein relates to a method for preparing an electrochemically active material, comprising: providing primary particles comprising soft carbon or natural graphite; adding the primary particles to a mixing system; adding an agglomerated aqueous solution having organic molecules to the mixing system, wherein the organic molecules are present in the solution at a concentration of about 0.1 wt % to about 40 wt % and the organic molecules are selected from lignin molecules, sugar molecules, lignin-carbohydrate complexes, and plant-derived carbohydrates; and mixing the agglomerated solution with the primary particles according to a predetermined standard to produce secondary particles having a particle size D50 of about 5 μm to about 1000 μm.

[0016] In some aspects, the technology described herein relates to a method wherein the primary particle is a soft carbon selected from micronized petroleum coke powder, polyvinyl chloride, mesophase pitch, pitch coke, or coal char.

[0017] In some aspects, the technology described herein relates to a method wherein the organic molecule is a sugar molecule and the sugar molecule is present in the solution at a concentration of about 1 wt % to about 20 wt %.

[0018] In some aspects, the technology described herein relates to a method further comprising drying the secondary particles, wherein the organic molecules are present in the secondary particles at about 0.1 wt % to about 5 wt % on a dry weight basis.

[0019] In some aspects, the technology described herein relates to a method wherein the mixing system is a high shear mixing system or a fluidization system.

[0020] In some aspects, the technology described herein relates to a method in which the concentration of organic molecules is varied throughout the mixing, and the organic molecule concentration is varied by the total agglomeration solution addition as a function of the ratio of primary particles used in the agglomeration.

[0021] In some aspects, the technology described herein relates to a method wherein the agglomeration solution has a pH of about 7 to 10 and the organic molecules include ammonium lignin sulfonate, sodium lignin sulfonate, alkali lignin, dealkalgin lignin, sucrose, ribose, nucleosides, glucose, glucosides, mannose, mannosides, galactose, galactosides, talitol, talosides, rhamnitol, rhamnoside, maltose, maltoside, lactoside, lactoside tetraacetate, 2,3-deoxy-2,3-dehydrolactose ... At least one of 2,3-dehydrolactose pentaacetate, 2,3-deoxylactose, glucuronic acid ester, N-acetylglucosamine, fructose, sorbose, 2-deoxygalactose, 2-deoxyglucose, maltulose, lactulose, palatinose, leucrose, trehalose, gentiobiose, isomaltose, maltulose, turanose, lactose, mannitol, sorbitol, dulcitol, xylitol, 1-aminosorbitol, isomalt, cellobiose, lactitol, maltitol and fructose.

[0022] In some aspects, the technology described herein relates to a method wherein the organic molecule is a lignin molecule and includes at least one of ammonium lignin sulfonate, sodium lignin sulfonate, alkali lignin, and dealkalized lignin.

[0023] In some aspects, the technology described herein relates to a method wherein the primary particles have a particle size D50 of about 5 μm to about 15 μm, and the secondary particles have a particle size D50 of about 10 μm to about 30 μm.

[0024] In some aspects, the technology described herein relates to a method wherein the agglomeration solution is an unsaturated solution.

[0025] In some aspects, the technology described herein relates to a method wherein the secondary particles are one of spherical, oblong, ellipsoidal, or almond-shaped and have a diameter of less than about 10 μm. 2 / g of BET surface area.

[0026] In some aspects, the technology described herein relates to a method that also includes heating the secondary particles to form the electrochemically active material.

[0027] In some aspects, the technology described herein relates to a method wherein the heating includes carbonizing at about 800°C to about 1200°C followed by graphitizing at about 2600°C to about 3000°C.

[0028] In some aspects, the technology described herein relates to a method wherein the electrochemically active material includes a matrix of soft carbon and hard carbon, wherein the ratio of soft carbon to hard carbon is from about 70:30 to about 99.5:0.5.

[0029] In some aspects, the technology described herein is directed to a method wherein the ratio of soft carbon to hard carbon is from about 97.5:2.5 to about 99.5:0.5.

[0030] In some aspects, the technology described herein relates to a method in which substantially all of the hard carbon content is derived from organic molecules.

[0031] In some aspects, the technology described herein relates to a method in which an electrochemically active material has a specific capacity greater than about 300 mAh / g in a battery half-cell.

[0032] In some aspects, the technology described herein relates to a method in which an electrochemically active material has a discharge capacity greater than about 340 mAh / g in a lithium-ion battery half-cell.

[0033] In some aspects, the technology described herein relates to a method in which both the primary particles and the secondary particles are not doped with additional inorganic particles.

[0034] In some aspects, the technology described herein relates to a method wherein the predetermined criteria include one or more of a high shear granulation pot speed, a high shear granulation mixing rotor speed, a residence time in the mixing system, an air flow rate, a nozzle spray interval, and a nozzle spray volume.

[0035] In some aspects, the technology described herein relates to a method wherein an agglomeration solution is sprayed into the mixture via a nozzle at a rate of about 12 mL / min per 500 grams of primary particles, and the agglomeration solution comprises about 2 wt % to about 30 wt % solids.

[0036] In some aspects, the technology described herein relates to a method in which the primary particles are not subjected to an oxidative treatment or a graphitization treatment prior to being added to the mixing system.

[0037] In some aspects, the technology described herein relates to a method wherein the primary particle is natural graphite.

[0038] In some aspects, the technology described herein relates to a method wherein the organic molecule is a sugar molecule and includes at least one of a monosaccharide, a disaccharide, and a polysaccharide of plant origin.

[0039] In some aspects, the technology described herein relates to an electrochemically active material comprising: artificial secondary particles, wherein the artificial secondary particles comprise one or more graphitized primary particles agglomerated together, the artificial secondary particles having a hard carbon content of about 0.2 wt % to about 4 wt %; and wherein the artificial secondary particles have a D50 of about 5 μm to about 50 μm; wherein the hard carbon content includes carbonized organic molecules, and the organic molecules are selected from lignin molecules, sugar molecules, lignin-carbohydrate complexes and plant-derived carbohydrates.

[0040] In some aspects, the technology described herein relates to electrochemically active materials wherein the artificial secondary particles have a particle size of less than about 10 μm. 2 / g of BET surface area.

[0041] In some aspects, the technology described herein relates to an electrochemically active material wherein the organic molecule comprises at least one of a monosaccharide, a disaccharide, or a polysaccharide.

[0042] In some aspects, the technology described herein relates to a battery comprising: a produced anode active material, a cathode active material; and a liquid electrolyte.

[0043] In some aspects, the technology described herein relates to a battery, wherein the battery is a lithium-ion battery or a sodium-ion battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 Shown is a SEM image of an exemplary agglomerated electrochemically active material with a scale bar of 50 microns.

[0045] Figure 2 Shown is a SEM image of agglomerated electrochemically active particles with a scale bar of 10 microns.

[0046] Figure 3 Shown is a schematic diagram of a high shear mixing system with counter-rotating disks.

[0047] Figure 4 A schematic diagram showing a fluidized bed reactor.

[0048] Figure 5 A schematic diagram of an additional fluidized bed reactor is shown.

[0049] Figure 6 Schematic diagram showing a flow diagram method according to embodiments herein. DETAILED DESCRIPTION

[0050] Disclosed herein is a method for preparing an electrochemically active material comprising graphite. The electrochemically active material includes secondary particles that can be agglomerated according to various methods disclosed herein. In some aspects, the agglomerated particles include primary graphite particles that are subjected to mixing with an agglomeration solution. The primary graphite particles can be natural graphite or soft carbon that can be converted into graphite during graphitization. The agglomeration solution can include a solvent having particles (e.g., organic particles) dissolved therein. In some cases, the agglomeration solution can be an aqueous solution in which organic molecules are dissolved.

[0051] In some aspects, agglomeration or mixing is performed in a mixing chamber configured to agglomerate primary particles that have been exposed to an agglomeration solution. In some embodiments, mixing or agglomeration is performed in a high shear or fluidized environment. For example, the mixing chamber can be a high shear mixing chamber or a fluidized chamber. Agglomeration processes can be performed continuously in these systems or produce secondary particles in an intermittent manner.

[0052] In a typical embodiment, the use of an aqueous agglomeration solution with plant-derived organic molecules promotes agglomeration of secondary particles that are equal or superior in quality to secondary particles of conventional origin produced according to conventional agglomeration processes. In addition, the use of plant-derived organic molecules allows for greater cost reduction and an environmentally friendly process that does not produce harmful or toxic byproducts.

[0053] In the embodiments described herein, the precursor powder for secondary particles or anode active materials may include synthetic materials or natural materials. Synthetic materials may include, but are not limited to, compositions produced via synthetic methods, or byproducts of chemical refining processes, such as powders derived from petroleum coke or coal tar. Synthetic graphite can be distinguished from natural graphite, although natural graphite materials can be replaced with synthetic graphite materials of the present disclosure. Similarly, the precursor powder can be a mixture of synthetic graphite and natural graphite. Synthetic materials may also be referred to as artificial materials. In some embodiments, the graphitization step can be omitted, and the secondary particles are subjected to carbonization heat treatment.

[0054] about Figure 1 , Figure 1An exemplary scanning electron microscope image of an agglomerated electrochemical material produced according to the methods disclosed herein is depicted. The lower right corner of the image shows a scale bar of 50 microns, thus showing that the agglomerated secondary particles produced in the embodiments of the present disclosure can have a diameter of less than 50 microns. The agglomerated particles can be composed of multiple primary particles agglomerated together. The image parameters are SED: 10 kV; WD: 12.4 mm; and STD: 3068.

[0055] Some embodiments herein may refer to the "average particle size" of primary or secondary particles. Average particle size should be given its ordinary meaning, as understood by those of ordinary skill in the art at the time of the present invention, but generally refers to the average of the largest dimensions of at least 20 random particles, as measured by direct observation by SEM and with a laser scattering particle size analyzer.

[0056] Figure 2 Depicted is an exemplary scanning electron microscope image of agglomerated secondary electrochemical particles prepared according to the methods disclosed herein. A scale bar of 10 microns is shown in the lower right corner of the image. Image parameters are SED: 10 kV; WD: 12.4 mm; and STD: 3071.

[0057] In the embodiments disclosed herein, the electrochemical particles include secondary particles heated, carbonized and / or graphitized at high temperatures, and can be used as anode materials in lithium ion batteries. The secondary particles are composed of two or more primary particles, and are agglomerated, granulated or kept together via agglomeration solution before heating. The primary particles can be provided in a high shear mixing system or a fluidized bed, and the agglomeration solution can be applied to the particles intermittently or continuously. The agglomeration solution includes particles that promote the agglomeration and bonding of the primary particles. The electrochemical particles or secondary particles can be observed via SEM and measured with a laser scattering particle size analyzer to determine physical properties, such as average particle size or median particle size.

[0058] As mentioned above, "agglomeration solution" is used to agglomerate primary particles. As understood by those of ordinary skill in the art, "agglomeration solution" should be given its general meaning, but may include, but is not limited to, a homogeneous or heterogeneous solution, an aqueous (water) solution, an alkaline aqueous solution, a miscible solution, an immiscible solution, a semi-organic solution, a semi-aqueous solution, an acidic aqueous solution, a fluid or viscous solution, or a substantially aqueous solution containing agglomerate particles dissolved or dispersed in a solvent. In the embodiments disclosed herein, the dissolved or dispersed particles in the agglomeration solution may be organic molecules. The term "organic" should be given its ordinary meaning that will be understood by those of ordinary skill in the art, but should include, but is not limited to, molecules consisting almost entirely of carbon, hydrogen, oxygen, and nitrogen. Organic molecules are different from inorganic compounds (which include transition metals, post-transition metals, lanthanides, actinides, alkali metals, alkaline earth metals, and metalloids of the periodic table). In some embodiments, the agglomerated particles may include lignin or lignin derivatives, sugars or sugar derivatives, or plant-derived carbohydrates.

[0059] In some embodiments, sugars may be dissolved in the agglomeration solution to promote agglomeration of primary particles according to the methods herein. The term "sugar" or "sugar solution" should be given its ordinary meaning as understood by those of ordinary skill in the art, but may include, but is not limited to, molecules or preparations containing all kinds of monosaccharides, disaccharides or polysaccharides, including dextrose, fructose, galactose, glucose, lactose, maltose or sucrose. The sugar solution may contain or be formulated from beet sugar, brown sugar, cane juice crystals, sucrose, castor sugar, coconut sugar, powdered sugar, corn syrup solids, crystallized fructose, date sugar, demerara sucrose, dextran, diastatic malt, ethyl maltol, Florida crystals, golden sugar, glucose syrup solids, dextrose, maltodextrin, muscovado, panela sugar, raw sugar, table sugar, sucanat, turbinado sugar, brown sugar, agave syrup / nectar, barley malt, blackstrap molasses, brown rice syrup, butter sugar / butter syrup, carob syrup, corn syrup, concentrated cane juice, golden syrup, high fructose corn syrup, honey, invert sugar, malt syrup, maple syrup, molasses, rice syrup, refined syrup, sorghum syrup, or treacle. Sugars can generally be described at the molecular level as having the general formula C n (H2O) n Any molecule of , where "n" can be any integer 1, 2, 3, 4, etc.

[0060] Unless otherwise indicated, the processes performed herein are deemed to be carried out at standard temperature and pressure of 25° C. and 1 atmosphere. Unless otherwise indicated, parts are parts by weight, temperatures are in° C., and pressures are in atmospheres.

[0061] The phrase "consisting essentially of" or "consists essentially of" should be interpreted as limiting the specified materials or steps involved (depending on the context), but should also include but not exclude any materials or steps that do not materially affect the basic and novel characteristics of the materials or steps involved.

[0062] The carbon source may be referred to as "hard carbon" or "soft carbon". These terms herein do not refer to the mineralogical hardness, but rather to the ability of the carbon to be converted into graphite. Hard carbon generally does not become graphitized and may have an amorphous structure. On the other hand, soft carbon has the ability to become graphite or be graphitized. In some embodiments, hard carbon may also be referred to as charcoal, charcoal, or non-graphitizable carbon.

[0063] In various embodiments, soft carbon can be composed of "artificial" particles. This term can be given as the ordinary meaning that will be understood by those of ordinary skill in the art, however, it should include but is not limited to artificial or synthetic or artificially separated particles, such as artificial graphite particles, which are composed via a synthetic method or are by-products of a chemical refining process or a chemical separation process, such as powders derived from petroleum coke or coal tar. Synthetic graphite can be distinguished from natural graphite, although natural graphite materials can be replaced with synthetic graphite materials of the present disclosure. "Graphite" particles can also be mentioned in various embodiments, and generally refer to particles composed of graphite, or can be converted into graphite via heating in a graphitization process.

[0064] In some embodiments herein, the agglomeration solution may be an "alkaline solution". This term should be given its ordinary meaning as understood by a person of ordinary skill in the art, but it may be interpreted as, but not limited to, a solution having a pH of 7 or higher. In various embodiments, the alkaline solution may have a pH of at least about 7, at least about 7.5, at least about 8, at least about 8.5, at least about 9, at least about 9.5, at least about 10, at least about 10.5, at least about 11, or any range therebetween. The alkaline solution may be formed by adding any molecule that increases the OH in the aqueous solution. - The term "solvent" refers to a solvent that has a higher concentration (under the Arrhenius definition), has a higher affinity for protons (under the Bronstead definition), or is an electron donor in an aqueous environment (under the Lewis definition). In various embodiments, the primary solvent in the solution is water, but there may be additional components and / or solvents mixed into the solution. For example, the solution may have a miscible solvent or other additive that reduces the polarity of the solution. In at least one embodiment, the solvent is an alkaline aqueous solution.

[0065] In embodiments herein, the agglomeration solution may be a "dispersion". As will be understood by those of ordinary skill in the art, the term should be given its common meaning, but may include, but is not limited to, a solution, a uniform dispersion, a non-uniform dispersion, a colloid, or a suspension. The dispersion may be a dispersion in any solvent, but the dispersion is typically an aqueous dispersion. The solvent may be a polar or non-polar solvent.

[0066] In some embodiments or examples herein, the agglomeration solution may include “lignin.” Lignin, typically derived from plant sources, is a complex polymer found in the cell walls of many plants and is the second most abundant organic material on earth after cellulose.

[0067] Lignin is beneficial because it reduces the cost of artificial graphite production, reduces the cost of battery cells, but does not react adversely with artificial primary particles or the resulting graphitized anode materials. Lignin can be synthesized, but is usually isolated from lignocellulose, which is composed of cellulose, hemicellulose, and lignin. Lignin can take many forms because lignin is a collection of highly heterogeneous polymers derived from a small amount of precursor lignin. The heterogeneity of lignin stems from the diversity and degree of cross-linking between these lignins.

[0068] There are usually three main types of lignin, called H, G and S lignin. These types of lignin are different in their chemical structure and are characterized by the type of monolignol units that constitute their polymer chains. The G unit is coniferyl alcohol (4-hydroxy-3-methoxyphenylpropane) and its group is sometimes called guaiacyl. The S unit is sinapyl alcohol (3,5-dimethoxy-4-hydroxyphenylpropane) and its group is sometimes called syringyl. The H unit is p-coumarol (4-hydroxyphenylpropane) and its group is sometimes called 4-hydroxyphenyl. H lignin is mainly composed of H units and is usually found in grasses and some dicots. G lignin is mainly composed of G units and is the most common type of lignin found in woody plants. S lignin is mainly composed of S units and is usually found in the secondary cell walls of hardwood. In addition, there are intermediate forms of lignin comprising a combination of H units, G units and S units, and the exact composition of lignin can vary according to plant species and tissue type. The intermediate separated lignin can be referred to as GS-lignin, wherein the lignin is mainly composed of GS monomer units and may have a small amount or not a large amount of H units. Other separated lignins may be HSG lignin, SH-lignin or HG-lignin. Lignin may also undergo modifications, such as hydroxylation, methylation and acetylation, which may affect its properties and functions. Therefore, embodiments in the present disclosure contemplate the use of hydroxylated, methylated or acetylated lignin or other modifications or functionalizations of lignin.

[0069] Lignin is usually insoluble in neutral aqueous solution. sp This means that K sp is less than 1, and is typically much less than 1 in neutral aqueous solution where the pH is about 7 or in solutions at a pH of 6.5 to 7.5. However, the solution or lignin can be modified to increase the solubility of the lignin so that its K sp Greater than 1 or much greater than 1, so that a significant amount of lignin is dissolved in an aqueous solution. For example, lignin can be dissolved by treating with an alkaline solution (such as sodium hydroxide or sodium sulfite). The resulting solution (called alkaline lignin) can be used as a raw material for embodiments of the present disclosure. Alternatively, lignin can be dissolved by treating with an acid (such as sulfuric acid). The acid hydrolysis process decomposes the lignin polymer into smaller fragments, resulting in a soluble lignin product that can be used in the embodiments disclosed herein. In addition, certain enzymes, such as laccase or peroxidase, can be used to modify the lignin structure, resulting in a more soluble product. Enzyme treatment can be used in combination with other methods to improve the lignin solubility in the embodiments disclosed herein. The embodiments disclosed herein contemplate the modification of any lignin molecule, such as the decomposition of lignin polymers into smaller fragments, or modification or lignin to increase the polarity of lignin molecules to increase their solubility in aqueous solvents or other polar solvents.

[0070] In some embodiments or examples disclosed herein, lignin can be dissolved by acid treatment, alkaline treatment, enzyme treatment or by functionalization or modification. In various embodiments, lignin can be dispersed alkaline lignin, which is sometimes referred to as lignin sulfonate. Lignin sulfonate is a group of lignin-based products produced by alkaline extraction of wood and other lignocellulosic materials. The alkaline extraction method includes treating lignocellulosic materials with a strong base (such as ammonia, sodium hydroxide or sodium sulfite), which decomposes the cell wall and releases lignin. The resulting lignin is then modified to produce lignin sulfonate, which is a water-soluble polymer with a wide range of industrial applications. Alkaline dispersed lignin has a negatively charged surface, making it very soluble in water and able to form a stable dispersion in an aqueous medium. The lignin sulfonate used in the various embodiments disclosed herein can be ammonium lignin sulfonate.

[0071] When evaluating the particles, the particle size distribution and sphericity can be measured by any suitable known technique, such as by SEM, optical microscopy, dynamic light scattering, laser diffraction, manual measurement of size using image analysis software (e.g., measuring at least three images of the same material portion or sample with about 15 to about 30 measurements per image), and any other technique.

[0072] The particle size distribution referred to herein can be expressed as "D50" or average particle size. The average particle size can be calculated as the average value of the particle distribution. D50 is also called the median particle diameter or median particle size. For example, for a powder sample with D50 = about 5 μm, this means that 50% of the particles are larger than about 5 μm and 50% of the particles are smaller than about 5 μm. In some embodiments, D50 can be evaluated as the sample size of an SEM image, for example, D50 is evaluated as the median particle size of 20 or more particles, or measured with a laser scattering particle size analyzer.

[0073] In some embodiments, the D50 of the secondary particles can be from about 1 micron to about 1000 microns, from about 1 micron to about 900 microns, from about 1 micron to about 700 microns, from about 1 micron to about 600 microns, from about 1 micron to about 500 microns, from about 1 micron to about 400 microns, from about 1 micron to about 300 microns, from about 1 micron to about 200 microns, from about 1 micron to about 100 microns, from about 1 micron to about 75 microns, from about 2 microns to about 40 microns, from about 5 microns to about 30 microns, from about 5 microns to about 20 microns, or from about 5 microns to about 15 microns. In a typical embodiment, the secondary particles have a diameter of about 10 microns to about 30 microns. In some embodiments, the secondary particles can be spherical or substantially spherical. In at least one embodiment, the secondary particles can be substantially spherical, oblong, elliptical or almond-shaped. The method described herein can provide secondary particles of various shapes, such as a mixture of substantially spherical, oblong, elliptical, almond-shaped or clustered particles.

[0074] The agglomerated spherical, elliptical, elongated or almond-shaped configuration of the secondary particles and the anode active material can promote the charge and discharge capabilities of the material. For example, the spherical or agglomerated shape of the secondary particles can enhance the packing properties, thereby enabling the formation of an active material layer with high density and increased capacity.

[0075] In some embodiments, the D50 of the primary particles can be from about 1 micron to about 75 microns, from about 1 micron to about 50 microns, from about 1 micron to about 45 microns, from about 1 micron to about 30 microns, from about 1 micron to about 20 microns, from about 1 micron to about 15 microns, from about 1 micron to about 10 microns, or from about 1 micron to about 5 microns. In a typical embodiment, the primary particles have a diameter of from about 1 micron to about 15 microns.

[0076] In various embodiments, the average particle size or D50 of the secondary particles can be about twice the D50 of the primary particles. The methods and embodiments disclosed herein enable the primary particles to be agglomerated or granulated to form secondary particles via agglomeration solutions (e.g., lignin solutions, sugar solutions, or solutions with non-graphitizable carbon) with organic molecules. The solution promotes aggregation, agglomeration, granulation, or agglomeration of the primary particles together, and plays the role of non-graphite or non-graphitizing hard carbon in the resulting anode active material.

[0077] The agglomeration solution described herein can have a concentration in terms of weight percentage or volume percentage. Unless otherwise specified, the parts shown are weight parts. The solution in the embodiment disclosed herein, such as an aqueous solution, can have organic molecules such as lignin or sugar that are dissolved in a higher percentage by increasing the temperature of the agglomeration solution. In various embodiments, the agglomeration solution can be heated so that it is at least about 22 degrees Celsius, at least about 25 degrees Celsius, at least about 28 degrees Celsius, at least about 30 degrees Celsius, at least about 40 degrees Celsius, at least about 50 degrees Celsius, at least about 60 degrees Celsius or any other range therebetween. The agglomeration solution with lignin molecules can have an increased solubility, wherein ammonium lignin sulfonate is dissolved therein, sodium lignin sulfonate is dissolved therein, or alkaline lignin is dissolved therein. Lignin was not used as an agglomeration material in the past due to its low solubility in aqueous solvents. The inventors of the present disclosure have found that lignin can be used as an agglomeration material for anode active materials, which is advantageous and unexpected considering the teachings of the prior art.

[0078] In various embodiments, the agglomeration solution can have a concentration of about 0.1wt% to about 40wt%, about 1wt% to about 30wt%, about 1wt% to about 20wt%, about 2wt% to about 18wt%, about 2wt% to about 15wt%, about 2wt% to about 12wt%, or about 8wt% to about 10wt%. In typical embodiments, the agglomeration solution is a solution in which organic molecules (such as lignin, sugar or plant-derived carbohydrates) are dissolved, and the solution contains about 7wt% to about 15wt% of lignin molecules. In various embodiments, the organic molecule is lignin, sugar or carbohydrate of plant origin.

[0079] The solution provided can be substantially pure to reduce contamination in the anode active material and promote the cleaning operation of the anode active material. Removing impurities in the solution, such as metals, can promote less side reactions or catalytic side reactions in the anode active material or the resulting battery cell. In various embodiments, the solution may include an acidic aqueous solution, an alkaline aqueous solution, an organic or non-polar solution, reverse osmosis water, ultrapure water, neutralized water, chemically filtered water, ion exchange water, water purified by a carbon block, water purified by activated carbon, or spring water. In various embodiments, water can be readily available tap water. In the embodiments disclosed herein, water may have a total dissolved solute (TDS) of less than about 500ppm, less than about 400ppm, less than about 300ppm, less than about 200ppm, less than about 100ppm, or less than about 50ppm.

[0080] In various embodiments, primary particles and agglomeration solution can be mixed and granulated via high shear mixing. High shear mixing system can adopt various forms and suitable high shear mixing, and agglomeration can be carried out with intermittent high shear system, online high shear system, powder injection high shear system, high shear granulator or powder injection high shear mixer. Intermittent high shear mixer can process large volume in a shorter time. On the other hand, online mixer is less prone to pollution and can be more effectively controlled. Generally, high shear system provides high shear force for particles in the system. Generally, the two main parts of high shear mixer are rotor and stator, which can be referred to as mixing head or generator. The area between rotor and stator, called shear gap, is an important area where the mixture is sheared. Therefore, mixing can be referred to as "high shear mixing". In some embodiments, the rotor can accelerate the fluid tangentially, and the inertia of the fluid prevents the fluid from flowing with the rotor. The fluid can flow to the shear gap or the area between the rotor tip and the stator. In the shear gap, there may be high speed difference and turbulent fluid flow, resulting in high shear rate.

[0081] In the embodiment of high shear mixing, the system should promote the mixing and agglomeration of primary powder particles and the addition of agglomeration medium or solution to produce secondary particles. The system can promote the progressive introduction of agglomeration solution or the continuous addition of agglomeration solution in primary particles. The system can be suitable for changing the type and concentration of agglomeration solution to provide different amounts or different concentrations of lignin, sugar or plant-derived carbohydrate molecules. For example, a highly concentrated agglomeration solution can be provided in the initial stage of mixing and agglomeration, followed by a solution of lower concentration, and vice versa. The concentration of agglomeration solution can be regulated or adjusted based on other parameters of the high shear system, such as the speed of air stream, mixing disk and mixing rotor and the residence time under various mixing conditions.

[0082] High shear mixer parameters can be optimized to promote primary particles of a specific size or secondary particles of a predetermined size. For example, primary particles can be processed or selected so that they have a particle size (D50) of about 1 micron to about 100 microns. Secondary particles can also be agglomerated so that they have a predetermined diameter (D50) of about 1 micron to about 100 microns. The predetermined diameter can depend on the use of the secondary particles as an anode active material. For example, in a specific battery cell with a predetermined electrochemical potential, larger particles may be optimal. The size of the secondary particles can be based on the charge / discharge characteristics of the battery cell.

[0083] In addition, the size of the secondary particles or the resulting anode active material can be controlled based on the type of ions or metals charged or discharged from the artificial graphite layer. For example, the size of the secondary particles can be controlled based on whether lithium ions / atoms, sodium ions / atoms, or other metal ions / atoms are configured to be intercalated or deintercalated with the graphite layer of the anode active material.

[0084] High shear granulation can be performed with or without primary particle size reduction. In various embodiments, micron-sized primary particles can be sieved and sized to a narrow size distribution before being placed in a high shear granulation system. In some embodiments, the primary particles can be larger particles that are broken down or sheared via a high shear system before agglomeration media is added to the system.

[0085] High shear systems can optimally promote agglomeration or granulation of primary particles. The agglomeration process can be described as a process of spraying or coating the particles with a solution, wetting the particles with the solution as the particles form agglomerates, and solidifying the agglomerated particles while partially or completely removing the agglomerate solution via heating.

[0086] Agglomeration time in a high shear system generally depends on system parameters, but can be at least about 30 seconds, at least about 1 minute, at least about 3 minutes, at least about 5 minutes, at least about 10 minutes, at least about 20 minutes, at least about 30 minutes, at least about 45 minutes, at least about 1 hour. In embodiments, the residence time is from about 5 minutes to about 30 minutes.

[0087] The parameters of the high shear mixing system can be adjusted before or during operation. For example, the speed of the mixing disk and the rotor can be adjusted relative to each other or relative to the residence time, and the residence time under each mixing condition can be changed. In the case where mixing and agglomeration result in oversized particles, the oversized particles can be removed and reduced in size to the target size via a classification system. In a typical embodiment, the target size of the secondary particles is 10 microns to 30 microns (μm).

[0088] Figure 3A high shear granulation system 30 with a rotating mixing disk 300 is depicted. The high shear granulation system 30 mixes material 306 with a rotor 304 moving in a counter-rotating direction 302. Thus, when material 306 encounters shear rotor 304, material 306 is subjected to shear forces. The high shear granulation system 30 shown here can be tilted so that gravity can be used to rotate the material in a circular or elliptical vortex. In various embodiments, the mixing chamber of the high shear mixing system can include ambient air, hypoxic ambient air, nitrogen, helium, argon or other inert gases. In some embodiments, the air can be filtered air to remove residual gas or vapor components and provide increased purity for the mixing process.

[0089] In this embodiment of the agglomeration process, the rotor 304 and the mixing disk 300 are initially set for counter-rotation. The speed can be set to about 5% of the maximum speed (about 5 rev / min to about 10 rev / min or RPM), while the total soft carbon material 306 is loaded into the mixer through the quantitative dosing port. The loading of the soft carbon material 306 should account for greater than about 30% but less than about 80% of the mixer volume. The mixer speed is then increased to about 50% of the total mixer speed (about 40RPM to about 60RPM). At this point, the agglomeration solution (which can include organic molecules, such as lignin, sugar or plant-derived carbohydrates, and is usually specified based on the final concentration) that forms hard carbon is slowly added to the mixture and becomes a part of the mixed material 306. The addition of the agglomeration solution occurs in at least about 30 seconds, at least about 1 minute, at least about 2 minutes, at least about 3 minutes or at least about 5 minutes. In a typical embodiment, the agglomeration solution is added in a time period of about 1 minute to about 2 minutes. After the total amount of agglomeration solution is added to the system, the mixer speed is increased to about 80% of the maximum speed (about 70RPM to about 90RPM). During this step, the agglomeration solution is more fully introduced into the soft carbon primary particles. Material 306 can be mixed at this speed for a time of about 0.1 minute to about 10 minutes, but in a typical embodiment, it is mixed for about 2 minutes, because two minutes of mixing are usually enough to introduce. Thereafter, the mixing can be optimized to micro-granulate. The rotation speed can reach about 10% of its maximum speed (about 10RPM to about 20RPM), which allows a snowball effect to be produced on the precursor particles rich in agglomerates. The mixing at about 10% of the maximum speed can vary and depends on the desired degree of agglomeration and micro-particle size. In some embodiments, the mixing can be at least about 1 minute, at least about 2 minutes, at least about 5 minutes, at least about 7 minutes, at least about 10 minutes, at least about 15 minutes, at least about 20 minutes, or at least about 30 minutes. In a typical embodiment, the mixing of this part is about 2 minutes to about 15 minutes. After this low speed mixing is completed, the resulting powder is then discharged from the mixer for further processing. The agglomerated material can then undergo a carbonization step in an inert atmosphere or a partially inert atmosphere to remove moisture and non-carbon elements. After carbonization, the material can be graphitized, and the primary soft carbon particles are converted into carbon with a graphite structure capable of lithium ion intercalation, and the hard carbon remains an amorphous structure.

[0090] In another embodiment, primary particles and agglomeration solution can be mixed and agglomerated via fluidization." fluidization " should be given the usual meaning as understood by those of ordinary skill in the art, but can include but not limited to by passing gas to the bed of solid particles, making it convert into a process of fluid-like state. There are various types of fluidization, and some examples can include bubbling fluidization, turbulent fluidization and circulating fluidization. Fluidization pressure can be high enough to offset the force of gravity on the particles, so that they float, suspend or respond in a fluidized bed.

[0091] Bubbling fluidization is a type of fluidization in which gas bubbles rise through a bed of solid particles, causing the particles to suspend and move. This type of fluidization is often used for small particles and low gas velocities. Bubbling fluidized bed reactors usually consist of a vertical vessel with a gas distributor at the bottom and a gas outlet at the top.

[0092] Turbulent fluidization is a type of fluidization in which a gas flows through a bed of solid particles at high velocity, causing the particles to become highly agitated and move rapidly. This type of fluidization can be used for larger particles and higher gas velocities, but can also be used for smaller particles that require thorough mixing, such as the particles of the present embodiment.

[0093] Circulating fluidization is a type of fluidization in which solid particles are lifted off the bottom of the bed by a gas and circulated throughout the bed. This type of fluidization can be used for large particles and high gas velocities. A circulating fluidized bed reactor typically consists of a vertical vessel with a gas distributor at the bottom, a gas outlet at the top, and a mechanism for lifting and circulating the solid particles.

[0094] In some embodiments, the fluidized device can be a spouted bed reactor. Spouted bed reactors can be used for coating processes and can involve the suspension of solid particles in a gas stream. These reactors typically consist of a vertical vessel with a gas inlet at the bottom and a gas outlet at the top and a mechanism for generating and controlling a gas stream through a bed of solid particles.

[0095] In some embodiments, the fluidized device can be a fixed bed reactor. Fixed bed reactors can be used for processes involving contact of a gas or liquid with a bed of solid particles. These reactors are typically composed of a horizontal or vertical vessel with a gas or liquid inlet at one end and a gas or liquid outlet at the other end.

[0096] In these fluidized systems, at least one nozzle or port can be used to provide agglomeration solution for fluidized particles. In some embodiments, the nozzle can be used to continuously spray the agglomeration solution in a stepwise manner, or can be used to spray the agglomeration solution based on the fluidization characteristics (such as air velocity, circulation speed, temperature, agglomeration particle size, etc.) of the fluidized reactor. In some embodiments, two nozzles can be provided, which are connected to agglomeration solutions of different concentrations. Therefore, each nozzle can provide agglomeration concentration based on the residence time in the fluidized system, the air velocity in the reactor, temperature, expected particle size, expected hard carbon content, etc.

[0097] Figure 4 Depicted is a fluidized bed system 40. In the system 40, compressed air is delivered to a heating system 408 through an inlet 410, and the heating system 408 heats the air. The compressed air can be ambient air, dry air, oxygen-reducing air, or an inert gas (e.g., nitrogen, helium, argon), etc. A fan 406 can be used to pressurize the air through a conduit leading to a fluidized bed surface 418 of a fluidized bed chamber 420. The pressurized air provides a fluidizing force for the fluidized particles 404. In this way, the fluidized particles 404, although solid particles, move as easily as they are fluids, which is why they are called "fluidized particles". A nozzle 412 provides agglomeration, particle coating, or a binder solution. The binder solution is maintained in a liquid container 400 and pumped to the nozzle 412 via a peristaltic pump 402. A filter 414 can be configured at the top of the fluidized bed to prevent vapor or fluidized particles from escaping. The filter 414 can be connected to an additional membrane that selectively filters steam or harmful gases to prevent them from escaping via an air outlet 416. Alternatively, a membrane for gases or harmful vapors may be included in the filter 414. After filtering, the gas particles may be released via the air outlet 416.

[0098] System 40 can be modified while still providing the above advantages. For example, compressed air can be an inert gas, such as helium, nitrogen, argon, etc. The gas can be heated via heating system 408, or the heating system can be turned off, and the gas can be a room temperature atmospheric gas. In addition, the circulation of fluidized particles can be promoted by rotors, blades, counter-rotating mixers, convection exhaust ports, conduits or other features to increase the uniformity of agglomeration solution or coating solution on fluidized particles 404. Agglomeration solution can be heated in liquid container 400 so that the amount of dissolved particles in agglomeration solution can be increased. This also provides such an advantage that the solution can be closer to the temperature of fluidized particles 404 and compressed gas. Fluidizing chamber 420 can be cylindrical, conical, truncated cone or any other shape to promote fluidization or convection or circulation of fluidized particles.

[0099] In an embodiment, primary particles or fluidized particles 404 are added to the fluidized bed chamber 420. The particles 404 are fluidized and allowed to reach a temperature of about 120°F to about 130°F before spraying begins.

[0100] Agglomeration solution (for example, solution comprising lignin, sugar or plant-derived carbohydrate) can be mixed together to produce a solution comprising about 1 wt % to 70 wt % solid, about 3 wt % to 20 wt % solid, about 3 wt % to 15 wt % solid, about 8 wt % to 15 wt % solid, at least about 3 wt % solid, at least about 5 wt % solid, at least about 8 wt % solid, at least about 10 wt % solid, at least about 15 wt % solid, at least about 20 wt % solid, at least about 30 wt % solid.Solid can be plant-derived organic molecules in agglomeration solution, such as sugar, plant-derived carbohydrate or lignin.In one embodiment, the components of agglomeration solution are heated so that the agglomeration solution comprises about 8 wt % to about 30 wt % solid.If the composition is too viscous to be sprayed via nozzle 412, the solution can be diluted.Alternatively, the material can be poured into fluidizing chamber 420, where a highly concentrated and viscous solution is required.

[0101] When the coating solution or agglomeration solution is sprayed from the nozzle 412, the solution can be heated and / or stirred in the liquid container 400. The coating solution or agglomeration solution can be sprayed into the bed at a rate of 12 mL / min per 500 grams of primary particles or soft carbon particles until the desired amount of solution is dispensed. In some embodiments, the coating of the particles can occur in several steps, wherein different concentrations or different agglomeration materials can be dispensed. For example, a first agglomeration solution containing about 3% to about 10% solids can be dispensed, followed by agglomeration solutions containing about 8% to about 12% solids. The nozzle can spray agglomeration solutions of fine mist or steam, such as spraying the nozzle with ultrasound. A temperature difference can be generated so that the agglomeration solution is hotter or colder than the temperature of the fluidized primary particles. The total amount of the coating solution or agglomeration solution varies based on the target concentration (based on dry basis) of the soft carbon precursor to form a binder with the hard carbon. In order to achieve microgranulation without over-wetting the precursor, a limited amount of agglomeration solution is dispensed, which can produce a muddy consistency. Therefore, the distribution of the agglomerated solution should be controlled according to various process parameters such as temperature, fluidization rate and air flow and desired particle size.After spraying is complete or threshold wetting is achieved, the resulting coated or agglomerated material is dried to about 125°F and then removed.

[0102] Fluidization of the agglomerated particles will cause most or all of the solvent to evaporate from the agglomerated solution due to the gas flow surrounding the fluidized material, leaving the lignin, sugar or plant-derived carbohydrate molecules surrounding the primary particles. In some embodiments, the gas flow in the fluidized bed can be adjusted to produce the desired amount of evaporation.

[0103] After the fluidized, granulated or agglomerated particles comprising hard carbon and soft carbon are discharged, they should contain a moisture content of less than about 0.25%. Therefore, in some cases, the particles may need to be further dried to reduce the total moisture content to less than about 0.25%. The dried and agglomerated material can then be further processed by calcination and graphitization to produce the final composite electrochemical material or anode material.

[0104] In a lithium ion battery half-cell, the agglomerated, calcined and graphitized anode material preferably has a D50 of about 10 μm to about 30 μm, a D50 of less than about 10 μm, and a D50 of less than about 10 μm. 2 / g BET surface area, a ratio of soft carbon to hard carbon of about 97.5:2.5 to about 99.5:0.5, and a discharge capacity greater than about 340 mAh / g. In various embodiments, the agglomerated particles are not doped with additional elements, such as silicon, and the primary particles are not ozone treated. In some embodiments, the secondary particles include elemental carbon, oxygen, and hydrogen, and exclude other metallic elements or inorganic elements. In some embodiments, the secondary particles are essentially composed of elemental carbon, oxygen, and hydrogen, and contain less than 1% metallic elements or inorganic elements.

[0105] refer to Figure 5 , shows a fluidizing device 50. The device is similar to Figure 4 50. However, the device may include a gas pressure source 506 for dispensing the agglomeration solution via the nozzle 502. The pressure source 506 may also be in the form of a peristaltic pump. The nozzle 502 may be a 35100 air atomizing nozzle. The pressure source 506 adjusts the pressure provided for dispensing the agglomeration solution. The fluidizing chamber 504 is depicted as a truncated cone, although other shapes or configurations may also be used. An outlet 510 for the fluidizing gas is provided on the top of the device 50. The parameters of the fluidization process can be modified via a user input terminal 508. Temperature, airflow, nozzle dispensing rate, pressure, humidity, air source, agglomeration solution concentration, fluidization time, mixing or convection parameters (where mixing blades or ducts are used) and other parameters can be adjusted via terminal 508.

[0106] System 50 can be modified while still providing the above advantages. In different embodiments, fluidizing chamber 504 can be configured so that the loading and removal of particles from fluidizing chamber 504 can be continuous. For example, a siphon can be provided at the top, middle or bottom of the fluidizing chamber in the fluidizing chamber, which can depend on convection parameters. The siphon can be used to siphon off secondary particles with a predetermined density, a coating threshold or a mean particle size. Meanwhile, a conduit can be connected to the fluidizing chamber to input uncoated primary particles, such as micronized petroleum coke powder. Therefore, a continuous agglomeration system can be achieved in this way.

[0107] Agglomerated secondary particles can be removed from the mixing equipment in various ways, including pouring out particles, siphoning out particles based on the density and sedimentation of the particles, screening particles, intermittently removing particles (in any of the methods described herein), pneumatically removing particles through a gas circulation system, or other particle removal methods known in the art. The particles can be removed after mixing and based on the desired particle size. In a typical embodiment, the agglomerated particles are removed after the particles have a particle size D50 of about 5 μm to about 1000 μm, preferably about 5 μm to about 30 μm.

[0108] The agglomeration solution can be a dispersed aqueous solution of lignin or a sugar solution, which can be incorporated via mixing. As described above, various drying and heating processes can substantially remove all liquids in the solution. Evaporation can be carried out in a high shear mixing system or a fluidized bed reactor. Evaporation can also be carried out in a heat treatment after the secondary particles are removed from the mixing system. In a typical embodiment, the heat treatment is a carbonization treatment carried out at about 800°C to about 1200°C to set the particle structure, followed by a graphitization treatment at about 2600°C to about 3000°C. In the graphitization treatment, artificial coke particles are converted into graphite particles, and non-graphitizable lignin, sugar or plant-derived carbohydrate molecules can be converted into hard carbon. After graphitization, the resulting material is an electrochemically active material and can be referred to as an anode active material, which can be included in a battery cell for an electrochemical process.

[0109] In embodiments herein, graphitization and carbonization can be performed in an inert or substantially inert environment or in the absence of water or oxygen. For example, the gas in the carbonization and graphitization chamber can be N2, CO2, helium, argon, krypton, xenon, or a mixture thereof. Alternatively, dry or oxygen-depleted ambient air can be used.

[0110] The carbonization temperature of the secondary particles can exceed the decomposition temperature of the carbonized molecules (e.g., organic molecules that form hard carbon). In some embodiments, TGA can be used to determine the decomposition temperature of organic molecules. For example, the carbonization temperature can exceed the decomposition temperature of lignin, lignin sulfonate, sucrose, glucose, fructose, dextrose, maltose, ribose, or any other synthetic or plant-derived carbohydrate.

[0111] The hard carbon content of the anode active material can vary according to the method for producing agglomerated secondary particles. For example, the hard carbon content can vary based on the amount of agglomeration solution added to the mixture, the amount of drying in the process, the concentration of the agglomeration solution, and the final particle size and structure. In some embodiments, the hard carbon content of the anode active material is about 0.01wt% to about 5wt%, about 0.1wt% to about 4wt%; about 0.2wt% to about 4wt%, about 0.3wt% to about 4wt%, about 0.5wt% to about 2.5wt%, about 0.5wt% to about 3.25wt%, or about 0.5wt% to about 3wt%. In typical embodiments, the hard carbon content is about 0.3wt% to about 2.5wt%, or preferably 1wt% to 1.5wt%. In some embodiments, the hard carbon content in the anode active material can be represented by a minimum hard carbon content, such as at least about 0.1wt%, at least about 0.2wt%, at least about 0.3wt%, at least about 0.4wt%, at least about 0.5wt%, at least about 1wt%, at least about 2wt%, or at least about 3wt%. In a typical embodiment, the hard carbon content is at least 0.3wt%. In embodiments disclosed herein, the hard carbon content is substantially derived from agglomeration solution, and artificial primary particles are substantially free of non-graphitizable hard carbon. In various embodiments, all hard carbons are derived from agglomeration solutions comprising organic molecules (such as lignin molecules, sugar molecules or plant-derived carbohydrate molecules). These organic molecules can be carbonized or pyrolyzed so that they constitute hard carbon.

[0112] Due to the reasons discussed above, the ratio of soft carbon to hard carbon in the anode active material can vary. Depending on the charge / discharge characteristics of the powder or the desired size of the secondary particles, it may be desirable to have more or less hard carbon. The soft carbon / hard carbon ratio may be about 60:40, about 65:35, about 70:30, about 75:25, about 80:20, about 85:15, about 90:10, about 95:5, about 97:3, about 98:2, about 99:1, about 99.9:0.9 or any number therebetween. In a typical embodiment, the ratio of soft carbon to hard carbon is about 97.5:2.5.

[0113] The structure of the agglomerated secondary particles can be verified during or after the mixing process. The size, shape, and surface area of ​​the particles can be observed via SEM and surface area analysis, such as BET (Brunauer-Emmett-Teller) surface area, or measured using a laser scattering particle size analyzer. The volume surface area of ​​the particles can vary depending on the desired particle size, but in typical embodiments, the BET surface area of ​​the secondary particles is less than about 10 m 2 In some embodiments, the volume surface area of ​​the secondary particles may be less than about 20 m 2 / g, less than about 15m2 / g, less than about 12m 2 / g, less than about 8m 2 / g, less than about 6m 2 / g, less than about 4m 2 / g or less than about 2m 2 In various embodiments, the surface area of ​​the secondary particles can be optimized to promote more embedding sites for lithium or sodium ions. For example, the BET surface area or specific surface area of ​​the secondary particles can be at least about 1 m 2 / g, at least about 2m 2 / g, at least about 3m 2 / g, at least about 4m 2 / g, at least about 6m 2 / g, at least about 7m 2 / g, at least about 8m 2 / g, or at least about 9m 2 / g.

[0114] BET surface area is a measure of the total surface available for adsorption on a porous material. Determination of the BET surface area can help understand the porosity, reactivity, and performance of a material. BET analysis assumes that gas molecules form a monolayer on the surface of a material at low relative pressures. As pressure increases, additional gas molecules are adsorbed in multiple layers on top of the monolayer. The theory provides a mathematical model to describe the adsorption behavior and calculate the surface area based on monolayer adsorption.

[0115] To determine the BET surface area, a sample of a porous material is exposed to different relative pressures of a specific gas, usually nitrogen. The amount of gas adsorbed at each pressure is measured. By plotting the adsorption isotherm and applying the BET equation, the surface area can be calculated. The BET surface area is expressed in square meters per gram (m 2 It is expressed in units of pore size distribution, specific surface area, and adsorption capacity of a material.

[0116] As shown above, embodiments of the present disclosure can produce anode active materials via a granulation method. The production of anode active materials from synthetic graphite can be carried out without additional inorganic dopants, such as silicon dopants. In addition, the production of anode active materials can be carried out, wherein the synthetic primary particles composed of soft carbon are not subjected to oxidation treatment before the granulation process. Before granulation, no additional treatment, such as graphitization of the synthetic primary particles composed of soft carbon, may be required.

[0117] The anode active materials of the present disclosure can be tested with a battery half-cell. A battery half-cell is a type of electrochemical cell that consists of one of two electrodes (usually an anode or a cathode) and an electrolyte solution. The other electrode, known as the counter electrode, is not included in the half-cell, but is provided by an external circuit. Half-cells are used in electrochemical experiments and measurements, where the behavior of a single electrode is studied separately. For example, a half-cell can be used to measure the voltage of a particular electrode, or to study its electrochemical reaction. Half-cells can also be used in practical applications, such as in the design and testing of battery systems. For example, a half-cell can be used to measure the voltage and capacity of a particular electrode, which can be used to optimize the design of the entire battery system.

[0118] The anode material produced herein may be included in an electrochemical cell (battery) or battery (cell). An electrochemical cell is a device that converts chemical energy into electrical energy and can be used to store and release electrical energy. It consists of one or more electrochemical cells, each of which contains two electrodes and a solid or liquid electrolyte. When an electric current is applied to the battery, a chemical reaction occurs at the electrodes, causing ions to flow through an electrolyte solution. This creates a potential difference or voltage between the electrodes, and the battery is able to store and release electrical energy. The voltage generated by the electrochemical cell depends on the material used for the electrode and the electrolyte, as well as the concentration of the electrolyte solution and other factors. The total reaction that occurs in the battery is a combination of independent reactions that occur in each of the electrochemical cells. Electrochemical cells are used in a wide range of applications, including portable electronic devices (such as smart phones and laptops), as well as cars, ships and backup power systems. They are widely used because they are relatively small, lightweight and rechargeable, making them very suitable for portable and mobile applications.

[0119] Figure 6 is a flow chart of an exemplary method for a method of making an electrochemically active material.

[0120] At step 610 , primary particles including soft carbon or natural graphite having a particle size D50 of about 1 μm to about 75 μm are provided.

[0121] At step 620, precursor particles are added to the mixing system.

[0122] At step 630, an agglomerated aqueous solution having organic molecules present in the solution at a concentration of about 0.1 wt% to about 40 wt%, and the organic molecules are selected from lignin molecules, sugar molecules, lignin-carbohydrate complexes, and plant-derived carbohydrates is added to the mixing system.

[0123] At step 640 , the agglomeration solution and the primary particles are mixed according to a predetermined standard to produce secondary particles having a particle size D50 of about 5 μm to about 1000 μm.

[0124] The embodiments or examples disclosed herein can be described in the following non-limiting terms.

[0125] Item 1. A method for preparing an electrochemically active material, the method comprising: providing primary particles comprising soft carbon or natural graphite, the primary particles having a particle size D50 of about 1 μm to about 75 μm; adding the primary particles to a mixing system; adding an agglomeration solution having organic molecules to the mixing system, the organic molecules being present in the solution at a concentration of about 0.1 wt % to about 40 wt %, and the organic molecules being selected from lignin molecules, sugar molecules, lignin-carbohydrate complexes, and plant-derived carbohydrates; and mixing the agglomeration solution with the primary particles according to predetermined standards to produce secondary particles having a particle size D50 of about 5 μm to about 1000 μm.

[0126] Item 2. The method according to Item 1, wherein the primary particles are soft carbon selected from micronized petroleum coke powder, polyvinyl chloride, mesophase pitch, asphalt coke or coal coke.

[0127] Item 3. The method according to Item 1 or 2, wherein the organic molecule is a sugar molecule, and the sugar molecule is present in the solution at a concentration of about 1 wt % to about 20 wt %.

[0128] Item 4. The method of Item 1, 2 or 3, further comprising drying the secondary particles, wherein the organic molecules are present in the secondary particles at about 0.1 wt % to about 5 wt % on a dry weight basis.

[0129] Item 5. The method according to claim 1 or 2-4, wherein the mixing system is a high shear mixing system or a fluidization system.

[0130] Item 6. A method according to claim 1 or 2-5, wherein the concentration of the organic molecule varies throughout the mixing, and the organic molecule concentration varies with the ratio of primary particles used in the agglomeration through the total agglomeration solution addition.

[0131] Item 7. A method according to item 1 or 2-6, wherein the agglomeration solution has a pH of about 7 to 10, and the organic molecules include ammonium lignin sulfonate, sodium lignin sulfonate, alkali lignin, dealkalgin lignin, sucrose, ribose, nucleosides, glucose, glucoside, mannose, mannoside, galactose, galactoside, talitol, taloside, rhamnitol, rhamnoside, maltose, maltoside, lactoside, lactoside tetraacetate, 2,3-deoxy-2,3-dehydrolactose, 2,3-deoxy -2,3-dehydrolactose pentaacetate, 2,3-deoxylactose, glucuronic acid ester, N-acetylglucosamine, fructose, sorbose, 2-deoxygalactose, 2-deoxyglucose, maltulose, lactulose, palatinose, leucrose, trehalose, gentiobiose, isomaltose, maltulose, turanose, lactose, mannitol, sorbitol, dulcitol, xylitol, 1-aminosorbitol, isomalt, cellobiose, lactitol, maltitol and at least one of fructose.

[0132] Item 8. The method of Item 1, 2, 4-5 or 6, wherein the organic molecule is a lignin molecule and comprises at least one of ammonium lignin sulfonate, sodium lignin sulfonate, alkali lignin and dealkalized lignin.

[0133] Item 9. The method according to Item 1 or 2-8, wherein the primary particles have a particle size D50 of about 5 μm to about 15 μm, and the secondary particles have a particle size D50 of about 10 μm to about 30 μm.

[0134] Item 10. The method according to Item 1 or 2-9, wherein the agglomeration solution is a homogeneous unsaturated solution.

[0135] Item 11. The method according to Item 1 or 2-10, wherein the secondary particles are one of spherical, oblong, elliptical or almond-shaped and have a diameter of less than about 10 m 2 / g of BET surface area.

[0136] Item 12. The method of Item 1 or 2-11, further comprising heating the secondary particles to form an electrochemically active material.

[0137] Item 13. The method of item 1 or 2-12, wherein the heating comprises carbonizing at about 800°C to about 1200°C, followed by graphitizing at about 2600°C to about 3000°C.

[0138] Item 14. A method according to item 1 or 2-12, wherein the electrochemically active material comprises a matrix of soft carbon and hard carbon, wherein the ratio of soft carbon to hard carbon is about 70:30 to about 99.5:0.5.

[0139] Item 15. The method of Item 14, wherein the ratio of soft carbon to hard carbon is from about 97.5:2.5 to about 99.5:0.5.

[0140] Item 16. The method of Item 1 or 2-14, wherein substantially all of the hard carbon content is derived from hydrocarbon molecules.

[0141] Item 17. The method of Item 1 or 2-12, wherein the electrochemically active material has a specific capacity in a battery half-cell of greater than about 300 mAh / g.

[0142] Item 18. The method of Item 12, wherein the electrochemically active material has a discharge capacity greater than about 340 mAh / g in a lithium ion battery half-cell.

[0143] Item 19. The method according to Item 1 or 2-18, wherein both the primary particles and the secondary particles are not doped with additional inorganic particles.

[0144] Item 20. A method according to Item 1 or 2-19, wherein the predetermined criteria include one or more of the speed of the high shear granulation pot, the speed of the high shear granulation mixing rotor, the residence time in the mixing system, the air flow velocity, the nozzle spray interval and the nozzle spray volume.

[0145] Item 21. The method of Item 1 or 2-20, wherein the agglomeration solution is sprayed onto the mixture via a nozzle at a rate of about 12 mL / min per 500 grams of primary particles, the agglomeration solution comprising about 2 wt% to about 30 wt% solids.

[0146] Item 22. The method according to Item 1 or 2-21, wherein the primary particles are not subjected to oxidation treatment or graphitization treatment before being added to the mixing system.

[0147] Item 23. The method of Item 1, 3-12, or 16-22, wherein the primary particles are natural graphite.

[0148] Item 24. The method of Item 1, 2-7, or 9-23, wherein the organic molecule is a sugar molecule and comprises at least one of a monosaccharide, a disaccharide, and a polysaccharide of plant origin.

[0149] Item 25. The method of Item 12, wherein the primary particles are natural graphite and the secondary particles are carbonized at a temperature of about 175°C to 1200°C without a graphitization step exceeding 1200°C.

[0150] Item 26. An electrochemically active material comprising: artificial secondary particles, wherein the artificial secondary particles comprise one or more graphitized primary particles agglomerated together, the artificial secondary particles having a hard carbon content of about 0.25 wt % to about 4 wt %; and wherein the artificial secondary particles have a D50 of about 5 μm to about 50 microns; wherein the hard carbon content comprises carbonized organic molecules, and the organic molecules are selected from lignin molecules, sugar molecules, lignin-carbohydrate complexes and plant-derived carbohydrates.

[0151] Item 27. An electrochemically active material according to Item 26, wherein the artificial secondary particles have a size of less than about 10 μm. 2 / g of BET surface area.

[0152] Item 28. An electrochemically active material according to Item 26 or 27, wherein the organic molecule comprises at least one of a monosaccharide, a disaccharide or a polysaccharide.

[0153] Item 29. A battery comprising: an anode active material, a cathode active material produced according to Item 1; and a liquid electrolyte.

[0154] Item 30. A battery according to Item 29, wherein the battery is a lithium ion battery or a sodium ion battery.

[0155] Item 31. A method for preparing an anode active material, comprising: providing primary particles comprising soft carbon and having a particle size D50 of about 1 μm to about 75 μm; adding the primary particles to a mixing system; adding a sugar aqueous solution to the mixing system, wherein the sugar aqueous solution is an unsaturated solution containing sugar molecules; and mixing the sugar aqueous solution and the primary particles according to a predetermined standard to produce secondary particles having a particle size D50 of about 5 μm to about 1000 μm.

[0156] Item 32. The method according to Item 31, wherein the sugar molecules are present in the aqueous sugar solution at a concentration of about 1 wt% to about 90 wt%.

[0157] Item 33. A method according to Item 31, wherein the sugar molecules are present in the aqueous sugar solution at a concentration of about 1 wt% to about 10 wt%.

[0158] Item 34. The method of Item 31 or 32, further comprising drying the secondary particles, wherein the sugar molecules are present in the secondary particles at about 3 wt % to about 20 wt % on a dry weight basis.

[0159] Item 35. The method of Item 31, 32 or 34, wherein the sugar molecule comprises at least one of a monosaccharide, a disaccharide and a polysaccharide of plant origin.

[0160] Item 36. A method according to Item 31, wherein the sugar solution has a concentration of about 1 wt% to about 10 wt%, the primary particles have a particle size D50 of about 5 μm to about 15 μm, and the secondary particles have a particle size D50 of about 10 μm to about 40 μm.

[0161] Item 36a. The method of Item 31, 32, or 34-35, additionally comprising heating the secondary particles at a temperature of about 800°C to about 1200°C to carbonize the sugar molecules, followed by graphitization at about 2600°C to about 3000°C.

[0162] Item 37. The method of Item 31-34 or 36-36a, wherein the sugar molecule comprises at least one of a monosaccharide and a disaccharide.

[0163] Item 38. An electrochemically active material comprising: secondary particles comprising one or more graphite primary particles agglomerated together, the secondary particles having a hard carbon content of about 0.25 wt % to about 4 wt %; and wherein the secondary particles have a D50 of about 5 μm to about 50 microns; wherein the hard carbon content comprises carbonized organic molecules selected from lignin molecules, sugar molecules and plant-derived carbohydrates.

[0164] Item 39. An electrochemically active material according to Item 38, wherein the secondary particles have a size of less than about 10 μm. 2 / g of BET surface area.

[0165] Item 40. An electrochemically active material according to Item 38 or 39, wherein the organic molecule comprises at least one of a monosaccharide, a disaccharide or a polysaccharide.

[0166] Item 41. An electrochemically active material according to Item 38 or 39-40, wherein the primary graphite particles are natural graphite.

[0167] Item 42. An electrochemically active material according to Item 38 or 39-40, wherein the primary graphite particles are synthetic graphite.

[0168] Item 43. An electrochemically active material according to item 38 or 39-42, wherein the secondary particles have a D50 of about 5 μm to about 30 μm.

[0169] Item 44. An anode active material comprising: secondary particles comprising one or more graphite primary particles agglomerated together by a carbonized hard carbon binder, the secondary particles having a hard carbon content of about 0.25 wt % to about 4 wt %; and wherein the secondary particles have a D50 of about 10 μm to about 30 microns; wherein the hard carbon binder content comprises carbonized organic molecules selected from sugar molecules and plant-derived carbohydrates.

[0170] Item 45. The anode material according to Item 44, wherein the secondary particles have a size of less than about 10 μm.2 / g of BET surface area.

[0171] Item 46. The anode material according to Item 44, wherein the secondary particles are composed of three or more primary particles agglomerated together via a carbonized hard carbon binder.

[0172] Item 47. An anode material according to Item 44 or 45, wherein the ratio of soft carbon to hard carbon is about 97.5:2.5 to about 99.5:0.5.

[0173] Item 48. An anode material according to Item 44 or 45-47, wherein the secondary particles consist essentially of graphite primary particles and a hard carbon binder.

[0174] Item 49. An anode material according to Item 44 or 45-47, wherein the hard carbon binder comprises carbonized glucose, sucrose or fructose.

[0175] Item 50. An anode material according to Item 44, 45-46 or 49, wherein the secondary particles consist solely of graphite primary particles and a hard carbon binder.

[0176] Item 51. The anode material according to Items 44, 45-49, wherein the secondary particles are free of inorganic molecules.

[0177] Item 52. The anode material according to Items 44, 45-49, wherein the secondary particles are composed of graphitic carbon and carbonized carbon.

[0178] Item 52. The anode material of Items 44, 45-49, wherein the secondary particles consist of carbon, oxygen and hydrogen, and do not include any other elements.

[0179] Item 53. A method for preparing an anode active material for a lithium-ion battery, the method comprising: providing primary particles having an average diameter or a median diameter of about 1 μm to about 30 μm; providing an agglomerated aqueous solution containing plant-derived molecules dissolved at about 0.1 wt % to about 40 wt %; mixing the primary particles with the agglomerated aqueous solution to obtain secondary particles having an average diameter or a median diameter of about 5 μm to about 30 μm; and heating the secondary particles at a carbonization temperature to convert the plant-derived molecules into hard carbon.

[0180] Item 54. A method according to Item 53, wherein the plant-derived molecules are separated from other organic substances.

[0181] Item 55. A method according to any one of Items 53-54, wherein the agglomeration solution is continuously provided from the nozzle.

[0182] Item 56. A method according to any one of Items 53-55, wherein the agglomeration solution is provided intermittently.

[0183] Item 57. A method according to any one of Items 53-56, wherein the particles are mixed in a high shear mixing system.

[0184] Item 58. A method according to any one of items 53-57, wherein the carbonization temperature is about 250 degrees Celsius to 1200 degrees Celsius.

[0185] Item 59. A method according to any one of items 53-58, wherein the carbonization temperature is about 250 degrees Celsius to 1200 degrees Celsius.

[0186] Item 60. The method of any one of Items 53-59, further comprising graphitizing the secondary particles at a temperature of about 2600°C to about 3000°C.

[0187] Item 61. A method according to any one of Items 53-60, wherein the plant-derived molecule satisfies the chemical formula C n (H2O) n , where "n" can be any positive integer.

[0188] Item 62. A method according to any one of items 53-61, wherein before dissolving the plant-derived molecules in the agglomeration solution, the water provided to the agglomeration aqueous solution has a TDS content of less than 200 PPM.

[0189] Item 63. A method according to any one of Items 53-61, wherein the plant-derived molecule is a disaccharide.

[0190] Item 64. A method according to any one of Items 53-61, wherein the plant-derived molecule is ammonium lignin sulfonate.

[0191] Item 65. A method according to any one of Items 53-64, wherein the particles are mixed in a high shear mixing system and the speed of the mixing disk is varied at least twice throughout the mixing process.

[0192] Item 66. The method of any one of Items 53-65, wherein the high shear mixing system is an intermittent high shear system, an in-line high shear system, a powder injection high shear system, a high shear granulator, or a powder injection high shear mixer.

[0193] Item 67. A method for preparing an anode active material for a lithium ion battery, the method comprising: providing primary particles having an average diameter or a median diameter of about 1 μm to about 15 μm; providing a sugar solution comprising about 0.1 wt % to about 40 wt % dissolved sugar molecules; and mixing the primary particles with an agglomeration aqueous solution to obtain secondary particles having an average diameter or a median diameter of about 5 μm to about 30 μm.

[0194] Item 68. The method of Item 67, further comprising heating the secondary particles at a temperature of about 400 to 1200 degrees Celsius and graphitizing at a temperature of about 1800 to 3000 degrees Celsius.

[0195] Item 69. The method of item 67, wherein the sugar solution comprises at least one of beet sugar, brown sugar, cane juice crystals, sucrose, castor sugar, coconut sugar, powdered sugar, corn syrup solids, crystalline fructose, date sugar, demerara sucrose, dextran, diastatic malt, ethyl maltol, Florida crystals, golden sugar, glucose syrup solids, dextrose, maltodextrin, muscovado, panela sugar, raw sugar, table sugar, sucanat, turbinado sugar, yellow sugar, agave syrup / nectar, barley malt, blackstrap molasses, brown rice syrup, butter sugar / butter syrup, carob syrup, corn syrup, concentrated cane juice, golden syrup, high fructose corn syrup, honey, invert sugar, malt syrup, maple syrup, molasses, rice syrup, refined syrup, sorghum syrup, or treacle.

[0196] Item 70. The method of Item 68 or 69, wherein the sugar solution is substantially free of impurities.

[0197] Item 71. The method according to Item 68 or 69-70, wherein the sugar solution consists essentially of water and a mixture satisfying the chemical formula C n (H2O) n where “n” can be any positive integer.

[0198] Item 72. A method according to any one of Items 68-71, wherein the secondary particles consist essentially of graphite and hard carbon.

[0199] Item 73. A method according to any one of Items 68-71, wherein the secondary particles consist solely of graphite and carbonized sugars, lignin or carbohydrates.

[0200] Example

[0201] The following is exemplary in nature to better illustrate the invention and is not limiting in scope, application, or use.

[0202] Example 1 - Micronized petroleum coke powder, polyvinyl chloride, mesophase pitch, pitch coke or coal char of particle size sufficient for lithium ion battery anode graphite is charged into a high shear granulation system. These primary particles have an average size of about 5 to about 15 μm.

[0203] Lignin, sugars or plant-derived carbohydrates (these contain non-graphitizable carbon) are diluted to allow for proper formulation and processing, and in embodiments, the lignin, sugars or plant-derived carbohydrates are dissolved so that the solution is unsaturated. The lignin, sugars or plant-derived carbohydrates can be diluted to about 3 wt % to about 15 wt % and added to the solvent mixture at a known rate for blending in the incorporation step.

[0204] Lignin, sugars or plant-derived carbohydrates can be used to adhere the primary particles to each other and to maintain the secondary particle structure through processing. The mass of lignin, sugars or plant-derived carbohydrates in the secondary particles can be greater than about 0.1% and less than about 10% (based on dry weight).

[0205] Once the agglomeration solution or binder addition is complete, the high shear system settings are adjusted to produce a granulated product with an average size of about 10 μm to about 30 μm. The speeds of both the disk and the mixing rotor are adjusted, as well as the residence time at each mixing condition.

[0206] The residence time of the mixture is selected based on the final granulation degree and the resulting agglomerate size and surface area. Agglomeration time depends on system parameters but ranges from about 5 minutes to about 30 minutes. Oversized particles are removed via standard classification methods and can be reduced to the target size range.

[0207] The resulting graphite / agglomerated molecular matrix is ​​then carbonized at about 800°C to about 1200°C to harden the material into its final form and produce a coke / hard carbon matrix.

[0208] Finally, the resulting particles may be graphitized from about 2600°C to about 3000°C to convert the coke structure to graphite and form a final synthetic graphite / hard carbon secondary particle composite.

[0209] Example 2 - Coke powder (derived from petroleum or coal tar) is micronized to have an average size of about 5 μm to about 15 μm.

[0210] Dilution of lignin, sugar or plant-derived carbohydrate to allow for proper formulation and processing.The lignin, sugar or plant-derived carbohydrate is diluted to about 2 wt% to about 12 wt% and added to the solvent at a known rate for blending in the incorporation step.

[0211] The coke powder is loaded into a fluidized bed granulation system and the bed is fluidized.

[0212] Aqueous lignin, sugar or vegetable carbohydrate binder can be added to the fluidized coke at a specified rate through a spray nozzle. The rate and total spray volume are determined by the target particle size and generally result in about 0.1% to about 10% lignin, sugar or vegetable carbohydrate mass on a dry weight basis.

[0213] When the coke powder particles are coated with the sprayed agglomeration solution, they will begin to adhere to each other by fluidization. This can be done in a continuous or intermittent fluidized bed granulator.

[0214] The process is continued until the agglomerated particles achieve a desired size (preferably a median particle size D50 greater than about 5 μm and less than about 30 μm) and a particle size less than about 10 μm. 2 / g of BET surface area.

[0215] The resulting agglomerated char / agglomerated particle matrix is ​​then carbonized at about 800°C to about 1200°C to harden the material into its final form and produce a coke / hard carbon matrix. Finally, the resulting particles are graphitized from about 2600°C to about 3000°C to convert the coke structure into graphite and form a final synthetic graphite / hard carbon secondary particle composite for use as an anode active material.

[0216] Example 3 - In a fluidized test batch, the parameters of the fluidizing equipment can be configured to have: 10 wt% to 12 wt% solid basis agglomerated into precursor particles, 12 mL / min nozzle rate, 200 ° F set point, 100 ° F to 150 ° F product temperature, 100-300 surface feet per minute (sfpm) fluidization velocity, 10 psi pressure, 2L fluidized bed, 500 g of petroleum coke precursor, 100 grams of 12% solid hard carbon agglomerate solution, and LS16 tube. The batch can be configured to have a 1 hour processing time for preheating, dosing, and drying. The nozzle used for coating is a 35100 air atomizing nozzle.

[0217] Additional Implementation

[0218] In the foregoing description, the present invention has been described with reference to specific embodiments of the present invention. However, it is apparent that various modifications and changes may be made thereto without departing from the broader spirit and scope of the present invention. Therefore, the description and drawings are to be regarded as illustrative rather than restrictive.

[0219] In fact, although the present invention has been disclosed in the context of certain embodiments and examples, it will be understood by those skilled in the art that the present invention extends beyond the specifically disclosed embodiments to other alternative embodiments and / or uses of the present invention and obvious modifications and equivalents thereof. In addition, although several variations of the embodiments of the present invention have been shown and described in detail, other modifications within the scope of the present invention will be apparent to those skilled in the art based on this disclosure. It is also conceivable that various combinations or sub-combinations of the specific features and aspects of the embodiments may be performed, and these combinations or sub-combinations still fall within the scope of the present invention. It should be understood that the various features and aspects of the disclosed embodiments may be combined or substituted with each other to form a variation pattern of the embodiments of the disclosed invention. Any method disclosed herein does not need to be performed in the order described. Therefore, the scope of the present invention disclosed herein should not be limited by the above-mentioned specific embodiments.

[0220] It should be understood that the systems and methods of the present disclosure each have several innovative aspects, no single innovative aspect of which is solely responsible for or required by the desired attributes disclosed herein. The various features and processes described above can be used independently of each other, or can be used in combination in various ways. All possible combinations and sub-combinations are intended to fall within the scope of the present disclosure.

[0221] Certain features described in this specification in the context of separate embodiments may also be implemented in combination in a single embodiment. Conversely, various features described in the context of a single embodiment may also be implemented in multiple embodiments individually or in any suitable sub-combination. In addition, although certain features may be used in certain combinations in the above description, and may even be initially claimed in such a combination, in some cases, one or more features may be removed from the claimed combination, and the claimed combination may be limited to a certain sub-combination or a variation thereof. Any single feature or feature group is not necessary or indispensable for every embodiment.

[0222] It should be understood that, unless otherwise specified or clearly defined in context, conditional language used herein (e.g., "can," "could," "might," "eg," etc.) is generally intended to indicate that certain embodiments include certain features, elements, and / or steps, while other embodiments do not. Thus, such conditional language is generally not intended to imply that one or more embodiments require features, elements, and / or steps in any way, or that one or more embodiments must include logic for determining whether these features, elements, and / or steps are included in or performed in any particular embodiment with or without author input or prompting. The terms "comprising," "including," "having," and the like are synonymous and are used in an open-ended sense, without excluding other elements, features, behaviors, operations, and the like. In addition, the term "or" is used in its inclusive sense (rather than in its exclusive sense), such that when used, for example, to connect a series of elements, the term "or" means one, some, or all of the elements in the list. In addition, the articles "a," "an," and "the" as used in this application and the appended claims should be construed to mean "one or more" or "at least one" unless otherwise indicated.

[0223] In addition, although the methods and devices described herein may have various modifications and alternative forms, specific examples thereof have been shown in the drawings and described in detail herein. However, it should be understood that the present invention is not limited to the specific forms or methods disclosed, however, the present invention will cover all modifications, equivalents and alternatives falling within the spirit and scope of the various embodiments described and the appended claims. In addition, any specific features, aspects, methods, properties, characteristics, qualities, attributes or elements, etc. disclosed herein in connection with an embodiment or implementation scheme can be used for all other embodiments or implementation schemes described herein. Any method disclosed herein does not need to be performed in the order described. The methods disclosed herein may include certain actions taken by a practitioner; however, the methods may also include any third-party instructions for those actions, whether explicitly or implicitly. The ranges disclosed herein also include any and all overlaps, sub-ranges and combinations thereof. Language such as "at most", "at least", "greater than", "less than", "between...", etc. includes the listed numbers. Numbers modified with terms such as "about" or "approximately" include the listed numbers and should be interpreted based on the circumstances (e.g., as accurate as reasonably possible under the circumstances, such as ±1%, ±5%, ±10%, ±15%, etc.). For example, "about 3.5 mm" includes "3.5 mm". Phrases modified with terms such as "substantially" include the recited phrase and should be interpreted based on the circumstances (e.g., as far as reasonably possible under the circumstances). For example, "substantially constant" includes "constant". Unless otherwise noted, all measurements are under standard conditions, including temperature and pressure.

[0224] As used herein, the phrase "at least one" of a list of items refers to any combination of those items, including single members. As an example, "at least one of A, B, or C" is intended to cover A, B, C, A and B, A and C, B and C, and A, B and C. Unless otherwise specifically stated, conjunction expressions such as the phrase "at least one of X, Y, and Z" are generally understood from the context to indicate that an item, term, etc. can be at least one of X, Y, or Z. Therefore, such conjunction expressions are generally not intended to imply that certain embodiments require at least one of X, at least one of Y, and at least one of Z to exist. The headings provided herein, if any, are for convenience only and do not necessarily affect the scope or meaning of the apparatus and methods disclosed herein.

[0225] Thus, the claims are not intended to limit the embodiments shown herein, but are to be accorded the widest scope consistent with this disclosure, the principles and the novel features disclosed herein.

Claims

1. A method for preparing an electrochemically active material, comprising: providing primary particles comprising soft carbon or natural graphite; adding the primary particles into a mixing system; adding an agglomerated aqueous solution having organic molecules to the mixing system, the organic molecules being present in the solution at a concentration of about 0.1 wt % to about 40 wt %, and the organic molecules being selected from the group consisting of lignin molecules, sugar molecules, lignin-carbohydrate complexes, and plant-derived carbohydrates; and The agglomeration solution is mixed with the primary particles according to a predetermined standard to produce secondary particles having a particle size D50 of about 5 μm to about 1000 μm.

2. The method according to claim 1, wherein the primary particles are soft carbon selected from micronized petroleum coke powder, polyvinyl chloride, mesophase pitch, pitch coke or coal coke. 3 . The method of claim 1 , wherein the organic molecule is a sugar molecule, and the sugar molecule is present in the solution at a concentration of about 1 wt % to about 20 wt %.

4. The method of claim 1, further comprising drying the secondary particles, wherein the organic molecules are present in the secondary particles at about 0.1 wt% to about 5 wt% on a dry weight basis.

5. The method of claim 1, wherein the mixing system is a high shear mixing system or a fluidizing system.

6. The method of claim 1, wherein the concentration of organic molecules varies throughout the mixing, and the organic molecule concentration varies with the ratio of the primary particles used in agglomeration through the total agglomeration solution addition.

7. The method of claim 1, wherein the agglomeration solution has a pH of about 7 to 10, and the organic molecules include ammonium lignin sulfonate, sodium lignin sulfonate, alkali lignin, dealkalgin lignin, sucrose, ribose, nucleosides, glucose, glucoside, mannose, mannoside, galactose, galactoside, talitol, taloside, rhamnitol, rhamnoside, maltose, maltoside, lactoside, lactoside tetraacetate, 2,3-deoxy-2,3-dehydrolactose, 2,3-dehydrolactose, 2,3-deoxy- ... At least one of 2,3-dehydrolactose pentaacetate, 2,3-deoxylactose, glucuronic acid ester, N-acetylglucosamine, fructose, sorbose, 2-deoxygalactose, 2-deoxyglucose, maltulose, lactulose, palatinose, leucrose, trehalose, gentiobiose, isomaltose, maltulose, turanose, lactose, mannitol, sorbitol, dulcitol, xylitol, 1-aminosorbitol, isomalt, cellobiose, lactitol, maltitol and fructose.

8. The method of claim 1, wherein the organic molecule is a lignin molecule and comprises at least one of ammonium lignin sulfonate, sodium lignin sulfonate, alkali lignin, and dealkalized lignin. 9 . The method of claim 1 , wherein the primary particles have a particle size D50 of about 5 μm to about 15 μm, and the secondary particles have a particle size D50 of about 10 μm to about 30 μm.

10. The method of claim 1, wherein the agglomeration solution is an unsaturated solution.

11. The method of claim 9, wherein the secondary particles are one of spherical, oblong, ellipsoidal, or almond-shaped and have a diameter of less than about 10 μm. 2 / g of BET surface area.

12. The method of claim 1, further comprising heating the secondary particles to form the electrochemically active material.

13. The method of claim 12, wherein the heating comprises carbonizing at about 800°C to about 1200°C, followed by graphitizing at about 2600°C to about 3000°C.

14. The method of claim 12, wherein the electrochemically active material comprises a matrix of soft carbon and hard carbon, wherein the ratio of soft carbon to hard carbon is from about 70:30 to about 99.5:0.

5.

15. The method of claim 14, wherein the ratio of soft carbon to hard carbon is from about 97.5:2.5 to about 99.5:0.

5.

16. The method of claim 14, wherein substantially all of the hard carbon content is derived from the organic molecules.

17. The method of claim 12, wherein the electrochemically active material has a specific capacity greater than about 300 mAh / g in a battery half-cell.

18. The method of claim 12, wherein the electrochemically active material has a discharge capacity greater than about 340 mAh / g in a lithium ion battery half-cell.

19. The method of claim 1, wherein both the primary particles and the secondary particles are not doped with additional inorganic particles.

20. The method of claim 1, wherein the predetermined criteria include one or more of a speed of a high shear granulation pot, a speed of a high shear granulation mixing rotor, a residence time in the mixing system, an air flow rate, a nozzle spray interval, and a nozzle spray volume.

21. The method of claim 1, wherein the agglomeration solution is sprayed into the mixture through a nozzle at a rate of about 12 mL / min per 500 grams of the primary particles, and the agglomeration solution comprises about 2 wt% to about 30 wt% solids.

22. The method of claim 1, wherein the primary particles are not subjected to an oxidation treatment or a graphitization treatment prior to being added to the mixing system.

23. The method of claim 1, wherein the primary particles are natural graphite.

24. The method of claim 1, wherein the organic molecule is a sugar molecule and comprises at least one of a monosaccharide, a disaccharide, and a polysaccharide of plant origin.

25. An electrochemically active material comprising: artificial secondary particles comprising one or more graphitized primary particles agglomerated together, the artificial secondary particles having a hard carbon content of about 0.2 wt % to about 4 wt %; and wherein the artificial secondary particles have a D50 of about 5 μm to about 50 μm; The hard carbon content comprises carbonized organic molecules, and the organic molecules are selected from the group consisting of lignin molecules, sugar molecules, lignin-carbohydrate complexes and plant-derived carbohydrates.

26. The electrochemically active material of claim 25, wherein the artificial secondary particles have a particle size of less than about 10 μm. 2 / g of BET surface area.

27. The electrochemically active material of claim 25, wherein the organic molecule comprises at least one of a monosaccharide, a disaccharide, or a polysaccharide.

28. A battery comprising: The anode active material produced according to claim 1, cathode active material; as well as Liquid electrolyte.

29. The battery according to claim 28, wherein the battery is a lithium ion battery or a sodium ion battery.

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