Sintered cathode active material element and method

Abstract

The present invention provides self-contained firing elements (e.g., bricks and tiles) containing a cathode active material. [Solution] A self-supporting firing element is provided, containing at least about 95% by weight of cathode active material.

Description

[Technical Field]

[0001] [Cross-reference of related applications] In the application data sheet or invoice submitted with this application, the foreign or domestic priority Any application with identified claims is a U.S. provisional application filed on September 22, 2020. No. 63 / 081,470, etc., 37 CFR 1.57, and Rule 4.18 and Incorporated herein by reference under 20.6.

[0002] This disclosure relates, in general terms, to electrode active materials and the process for forming them. More specifically, this disclosure The disclosure relates to the formation of metal oxide cathode materials for lithium-ion batteries. [Background technology]

[0003] The calcination of metal oxide cathode active materials is typically performed through a large roller hearth kiln. This involves baking a powdered material at high temperatures to obtain the desired material properties. Seth starts as a mixture of lithium compounds and metal precursors and forms a powder mixture. The end is typically carried in a sheath (i.e., a large ceramic crucible), and then this Cathode precursor powder is supplied to a high-temperature kiln for a total residence time exceeding 12 hours. An illustrative schematic diagram of a pod holding the end shows a cathode powder height of approximately 80 mm and approximately 0.9 k g / m 3 The bulk density is shown in Figure 1. The reacted material is then removed from the pod. The material is ground to the target particle size and optionally undergoes a surface treatment process before being supplied to the electrode manufacturing process. To receive.

[0004] However, the firing process is the most common in roller hearth kilns (RHKs) Due to high capital costs, the highest energy consumption, and long residence time, all professionals This accounts for the highest portion of the manufacturing costs within the Seth. As a result, the processing capacity of these kilns Maximizing this is important for reducing the capital and operating costs of cathode manufacturing. .

[0005] Furthermore, the sheath itself introduces inefficiencies into the firing process. The standard dimensions of the sheath for RHK are The dimensions are 100mm x 330mm x 330mm (H x W x L), and the usable height is ≤80m The quantity is m, and the total weight per pod exceeds 5 kg. The typical bulk density of the powder mixture is approximately 0. 9 g / cm³ 3 Typically, each pod can only be filled with approximately 4.5 kg of mixed material. Furthermore, high loads can affect gas diffusion and heat distribution, potentially leading to quality problems. Productivity is improved by stacking the stalks on top of each other (in a typical industrial kiln configuration, This is achieved by being able to accommodate four rows of pods stacked in parallel in two layers. While it is possible, such productivity strategies are not scalable.

[0006] Thus, the pod has many inherent inefficiencies, including: 1) the powder in the crucible As a result of stagnation, the heat and mass transfer coefficients are low, and the required residence time in the kiln is further reduced. 1) Increased cooling time at the kiln outlet prevents sheath cracking and extends sheath life. 3) The sheath usually needs to be replaced after 1-2 weeks of use, so wear and tear High cost of goods; 4) The handling and inspection system for sacks is highly capital-intensive and requires frequent... This could cause delays.

[0007] Furthermore, the firing process may include further treatment to improve the crystallinity of the active material. Improvements in quality crystallinity typically correlate with improvements in the performance of energy storage devices, Further processing to improve crystallinity introduces further inefficiencies into the manufacturing process. [Overview of the project]

[0008] For the purpose of summarizing the benefits achieved beyond this disclosure and prior art, this disclosure is intended to serve specific purposes. The benefits and advantages described herein are not applicable to any specific purpose or advantage. This cannot be achieved in the embodiments described above. Therefore, for example, those skilled in the art will understand the present invention. However, this does not necessarily achieve any other purpose or benefit that may be taught or suggested herein. Rather than achieving or optimizing one or more advantages as taught herein, They will recognize that it can be materialized or implemented in this way.

[0009] All of these embodiments are intended to fall within the scope of the invention disclosed herein. These and other embodiments are described below in the attached drawings as preferred embodiments. As will be readily apparent to those skilled in the art from the detailed description, the present invention is disclosed in any particular preferred manner. The embodiments are not limited to those described above.

[0010] In one embodiment, a self-supporting firing element is described. The self-supporting firing element is at least about 95 Contains a cathode active material in a weight percentage.

[0011] In some embodiments, the cathode active material comprises crystalline cathode active material particles. In one embodiment, the cathode active material is lithium nickel manganese cobalt oxide (N MC), lithium manganese oxide (LMO), lithium iron phosphate (LFP), lithium co Baltic oxide (LCO), lithium titanate (LTO), lithium nickel manganese oxide Lithium-ionized metal (LNMO), lithium nickel-cobalt aluminum oxide (NCA), nickel-ma Aluminum oxide (NMA), nickel-cobalt-manganese aluminum oxide ( Selected from the group consisting of NMCA, LiNiO2, or combinations thereof. In one embodiment, the self-supporting firing element contains a maximum of approximately 1% by weight of residual lithium. In some embodiments, the self-supporting firing element contains approximately 0.1 to 1% by weight of binder. In some embodiments, the freestanding firing element substantially does not contain a binder.

[0012] In some embodiments, the self-supporting firing element includes multiple through holes. In its form, the self-supporting firing element includes 2 to 50 through holes. In some embodiments, Each of the multiple through holes has a diameter of approximately 10-30 mm. In some embodiments, it is self-supporting. The fired elements contain multiple through-holes, accounting for approximately 0.1-30% of the total element volume. Several implementations In this state, the freestanding fired elements form at least one channel between adjacent elements. Includes a surface pattern configured as follows. In some embodiments, the freestanding firing element is It is in the shape of a lantern or tile. In some embodiments, the freestanding firing element is about 1. 9-2.3 g / cm³ 3 It includes the density of. In some embodiments, the freestanding firing element is about 1.7~1.8 g / cm³ 3 It includes the density of.

[0013] In another embodiment, a process for preparing a cathode active material is described. This involves mixing a reagent with a metal precursor to form a precursor mixture, and then compressing the precursor mixture. To create a self-supporting precursor element, and to heat the self-supporting precursor element to include the cathode active material. This includes forming self-contained firing elements.

[0014] In some embodiments, the reagent is a lithium reagent. The Um reagents include lithium hydroxide, lithium hydroxide monohydrate, lithium carbonate, and their Selected from a group consisting of combinations. In some embodiments, the metal precursor is a metal acid Selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, and combinations thereof. In some embodiments, the metal precursor is Ni, Mn, Co, Al, Mg, Fe, Ti This includes metals selected from the group consisting of combinations thereof.

[0015] In some embodiments, the precursor mixture further comprises a solvent. In some embodiments, The solvent is water. In some embodiments, the precursor mixture is about 0.1 to 20% by weight. It contains a solvent. In some embodiments, the precursor mixture further contains a binder. In one embodiment, the binder is poly(ethylene glycol) (PEG), poly(ethylene glycol) Thiene oxide (PEO), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyacrylic acid (PAA), methylcellulose (MC), carboxymethyl Cellulose (CMC), CMC salt, hydroxypropylcellulose (HPC), hydroxypropyl Cethylcellulose (HEC) and hydroxypropylmethylcellulose (HPMC) ), polytetrafluoroethylene (PTFE), and groups consisting of combinations thereof. Selected from. In some embodiments, the precursor mixture contains about 0.1 to 1% by weight of bi. Contains a buffer. In some embodiments, the precursor mixture contains about 0.025 to 1% by weight of a buffer. It contains inder. In some embodiments, the freestanding precursor element includes a plurality of through holes. In some embodiments, the process involves stacking multiple freestanding precursor elements to form elements. Further includes forming a tack. In some embodiments, the element stack is adjacent to It includes at least one channel between the independent precursor elements. In some embodiments, The independent precursor element is approximately 1.9-2.3 g / cm³. 3 It includes the density of.

[0016] In some embodiments, the freestanding precursor element is supported by the substrate while being heated. In some embodiments, the self-supporting precursor element, when heated, undergoes high-temperature tunnel killing. It is transported through a vent. In some embodiments, heating is performed in an oxidizing atmosphere, an inert atmosphere The process is carried out in an atmosphere selected from the group consisting of a reducing atmosphere and several implementations. In this configuration, heating is carried out in an oxygen-containing atmosphere. In some embodiments, heating is about 6 The process is carried out at temperatures of 50 to 850°C. In some embodiments, the process is carried out using an independent precursor. The process includes preheating the body elements. In some embodiments, the process involves the cathode active material It does not involve any additional heating steps.

[0017] In some embodiments, the process involves destroying the freestanding calcined elements to form calcined element powder. It further includes doing. In some embodiments, destruction is crushing, grinding, and those The process includes a step selected from a group consisting of combinations. In some embodiments, the process The process further includes processing the cathode active material. In some embodiments, the process is From the group consisting of sieving, washing, filtration, drying, coating, and combinations thereof Includes the selected steps.

[0018] In another embodiment, a process for forming a cathode electrode is described. The cathode active material described herein is incorporated into the electrode film, and the electrode film is placed on the current collector. This includes doing.

[0019] In another aspect, a process for forming an energy storage device is described. Seth houses the separator, anode electrode, and cathode electrode described herein within the housing. The separator is positioned between the anode electrode and the cathode electrode, including the placement of the separator between the anode electrode and the cathode electrode. In some embodiments, the energy storage device is a battery. [Brief explanation of the drawing]

[0020] [Figure 1] This is a schematic diagram of a conventional cathode precursor powder held in a sheath.

[0021] [Figure 2A] Images of dried bricks formed according to several embodiments are shown.

[0022] [Figure 2B] Images of the dried bricks shown in Figure 2A after they have collapsed following baking, according to several embodiments, are shown.

[0023] [Figure 2C] Images of self-supporting bricks formed with water and binder according to several embodiments are shown.

[0024] [Figure 2D]Images of the self-supporting bricks after baking in several embodiments are shown in Figure 2C.

[0025] [Figure 3A] This is a schematic diagram of a self-supporting precursor brick having multiple through holes according to several embodiments.

[0026] [Figure 3B] Figure 3A is a schematic diagram of a self-supporting precursor brick stack according to several embodiments.

[0027] [Figure 3C] This is a schematic diagram of a self-supporting precursor tile according to several embodiments.

[0028] [Figure 3D] Figure 3C is a schematic diagram of a stack of freestanding precursor tiles according to several embodiments.

[0029] [Figure 4] This flowchart shows the process of forming a cathode material through a formation process according to several embodiments.

[0030] [Figure 5A] Images of press-formed precursor bricks according to several embodiments are shown.

[0031] [Figure 5B] Images of pre-baked bricks according to several embodiments are shown.

[0032] [Figure 5C] Images of fired bricks that retain their shape through firing processes according to several embodiments are shown.

[0033] [Figure 5D] Images of fired bricks that have lost their shape through firing processes according to several embodiments are shown.

[0034] [Figure 6A] Images of fired tiles that retain their shape through firing processes according to several embodiments are shown.

[0035] [Figure 6B] Images of fired tiles that have lost their shape through the firing process according to several embodiments are shown. Detailed description of the invention

[0036] Various embodiments for preparing cathode active materials with improved crystallinity are provided herein. In certain embodiments, freestanding precursor elements (e.g., bricks and tiles) are formed. ...heated, self-firing elements containing cathode active material (e.g., bricks and tiles) This generates the cathode active material, and the cathode active material shows improved crystallinity. For example, in some embodiments, A mixture of lithium and metal powder is a self-supporting or self-supporting element (e.g., a brick and It is formed into tiles and then transported through a high-temperature furnace. In some embodiments, Elements (e.g., precursors, pre-baked elements and / or fired elements) are bricks and / or Alternatively, it may be any freestanding geometric shape or form, such as a tile.

[0037] The use of freestanding elements (e.g., bricks and tiles) removes sheaths from the manufacturing process. This enables the following improvements in manufacturing: 1) the body of the sintering process 1) Increased efficiency; 2) Increased processing capacity of typical industrial kilns; 3) Heating in each cycle 4) A decrease in the amount of heat that needs to be cooled; 5) An increase in the thermal conductivity of the powder mixture supplied to the furnace. 5) Increased thermal uniformity; 6) Reduced required process residence time; 7) Support geometry Reducing consumable costs by simplifying the shape (e.g., sheath to plate). Precursor mixture

[0038] Prior to the formation of the elements, in one embodiment, a precursor mixture comprising reagents and metal precursors is formed . In some embodiments, the reagent is a lithium reagent. In some embodiments , the lithium reagent is selected from lithium hydroxide, lithium hydroxide monohydrate, lithium carbonate, and combinations thereof . In some embodiments, the metal precursor is a metal oxide (M x O n ), a metal hydroxide (M x (OH) n ), a metal carbonate (M x (CO3) n ), and combinations thereof, where "M" represents a metal and "x" and "n" are values that create a charge-neutral metal precursor . In some embodiments, the metal precursor is a metal selected from Ni, Mn, Co, Al, Mg, Fe, Ti, and combinations thereof (the "" [[ID=,31]]n M").

[0039] * In some embodiments, the precursor mixture further comprises a solvent. In some embodiments , the solvent can help maintain the shape of the elements formed from the precursor mixture through the firing process . In some embodiments, the solvent is water. In some embodiments, the precursor mixture comprises 0.1 wt%, 0.5 wt%, 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt% or 30 wt% of the solvent, or about 0.1 wt%, 0<0000 =444>.5 wt%, 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt% or 30 wt% of the solvent, or any range of values therebetween. In some embodiments ​Therefore, the precursor mixture does not contain or substantially contains the solvent or added solvent. No. In some embodiments, the precursor mixture does not contain water or added water. , or substantially without. For example, in some embodiments, water or added water The precursor mixture, which is substantially free of water, may contain water absorbed from atmospheric moisture.

[0040] In some embodiments, the precursor mixture further comprises a binder. Morphologically, the binder is the shape of the elements formed from the precursor mixture through the calcination process. It may help maintain [the property]. In some embodiments, the binder includes a polymer material. In some embodiments, the binder includes a water-soluble polymer material. In this state, the binder is poly(ethylene glycol) (PEG), poly(ethylene oxy Polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), Polyacrylic acid (PAA), methylcellulose (MC), carboxymethylcellulose ( CMC) and their salts (e.g., sodium CMC), hydroxypropylcellulose Hydroxyethylcellulose (HEC), hydroxypropylmethylcellulose (HPC), and hydroxypropylmethylcellulose Cellulose (HPMC), polytetrafluoroethylene (PTFE), and related materials The polymer material includes a polymer material selected from a combination of these materials. In some embodiments, the polymer material The prices are 20,000, 25,000, 28,000, 30,000, 40,000, 50,000, 6 0000, 70000, 80000, 90000, 100000, 110000, 120 0000, 1300000, 1400000, 1600000 or 2000000, Or approximately 20,000, 25,000, 28,000, 30,000, 40,000, 50,000, 60000, 70000, 80000, 90000, 100000, 110000, 12 00000, 1300000, 1400000, 1600000, or 2000000 It has a weight-average molecular weight of any range of values ​​between them. In some embodiments, The precursor mixture is 0.01% by weight, 0.02% by weight, 0.025% by weight, and 0.3% by weight. , 0.04% by weight, 0.05% by weight, 0.06% by weight, 0.07% by weight, 0.08% by weight , 0.09% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5 Weight%, 0.6% by weight, 0.7% by weight, 0.8% by weight, 1% by weight, 1.2% by weight, 1.5 Weight percent or 2% by weight, or approximately 0.01% by weight, 0.02% by weight, 0.025% by weight, 0.3% by weight, 0.04% by weight, 0.05% by weight, 0.06% by weight, 0.07% by weight, 0 .08wt%, 0.09wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt Amount%, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 1% by weight, 1.2% by weight Binders with values ​​of % by volume, 1.5% by weight, 2% by weight, or any range in between. Includes.

[0041] In some embodiments, the precursor mixture further comprises additives. The additives include elements selected from Fe, Ti, and combinations thereof. Precursor and calcination elements

[0042] From the precursor mixture, precursors or raw elements are formed, and the elements are self-supporting or It can stand on its own. In some embodiments, the self-supporting precursor brick is pre-baked or In the preheating step, it is heated to form self-supporting pre-baked elements. Furthermore, then, self-supporting The precursor or pre-baked element is heated to react with the reagent and the metal precursor, and a self-contained calcination is performed. It can form constituent elements, and the calcined elements contain a cathode active material. The precursor elements are It contains the same or substantially the same composition as the precursor mixture that is formed. It is self-supporting or not self-supporting. Elements are understood as elements that maintain their shape and structure by their own weight.

[0043] Figures 2A and 2B show water- and binder-free blends according to several embodiments. These are photographic images of a moth, and Figures 2C and 2D show water and vinegar according to several embodiments. This is an image of bricks containing dart. Figure 2A shows a mixture without water and binder. The formed dried bricks are formed into self-supporting precursor bricks. In this embodiment, the precursor Body bricks are 1.7 g / cm³ 3 It was found to have the density of Figure 2A. The dried bricks did not maintain the formed brick structure and collapsed over time, as shown in Figure 2B. In contrast, Figure 2C shows approximately 1.8 g / cm³. 3 Contains water and a binder formed at a density of A brick is shown. This brick substantially maintains its structure over time, as shown in Figure 2D. It was found that the bricks shown in Figures 2C and 2D are self-supporting as described herein. It can be considered that this is the case.

[0044] In some embodiments, the freestanding precursor element includes multiple through-holes. Figure 3A shows This is a schematic diagram of a self-supporting precursor brick containing multiple through-holes according to several embodiments. Figure 3 B shows such self-supporting precursor bricks, each containing multiple through-holes, stacked in sequence. This is a schematic diagram. In some embodiments, the freestanding precursor elements are stacked. This includes a surface pattern such that at least one channel is formed between adjacent elements. nothing.

[0045] Figure 4A shows an overview of a self-supporting precursor tile having a wavefront pattern according to several embodiments. This is a schematic diagram. Figure 4B shows the space between adjacent stacked tiles when tiles are stacked. Such an independent precursor having a wavefront pattern in which multiple channels are formed This is a schematic diagram of Il.

[0046] Precursor elements (or any form, e.g., precursor, pre-baked, calcined, or disclosed) During any other step of the process, at least one channel is stacked. It includes at least one through-hole and / or surface pattern that enables the formation of i. Such through holes and / or channels between stacked bricks or tiles. This includes exposure to air (e.g., an oxidizing atmosphere (e.g., one containing oxygen), an inert atmosphere, and (A reducing atmosphere) can facilitate diffusion and moisture release from elements. For example, precursors Oxygen diffusion into the element helps consume oxygen as part of the reaction that forms the cathode active material. Through holes and / or channels are formed, and O2 is tested within the element and / or at the center of the element. This may allow access to the drug, while the rest of the element maintains a high packing density. This makes it possible. Furthermore, H2O is produced as part of the reaction that forms the cathode active material. Therefore, through holes and / or channels allow moisture to enter from the inside and / or center of the element. This can allow leakage, thereby resulting in the final material properties of the element after heating. For example, in some embodiments, through holes and / or channels are required after baking. It can prevent cracks from forming.

[0047] In some embodiments, the freestanding precursor elements are 2, 4, 6, 8, 10, 12, 15 , 20, 25, 30 or 50 through holes, or approximately 2, 4, 6, 8, 10, 12, 1 Through holes of 5, 20, 25, 30, or 50, or any range of values ​​between them. Includes holes. In some embodiments, each of the multiple through holes has a diameter of 1 mm, 5 mm, 1 0mm, 15mm, 20mm, 25mm, 30mm, 40mm, 50mm, 75mm The lengths are 100mm, or approximately 1mm, 5mm, 10mm, 15mm, 20mm, 25mm. 30mm, 40mm, 50mm, 75mm, or 100mm, or any in between. The value is within the range of . In some embodiments, each of the multiple through holes is accessible from the other through holes. 10mm, 11mm, 12mm, 13mm, 14mm, 15mm, 17mm, 20mm, 25mm, 30mm, 35mm, 40mm, 45mm, 50mm, 60mm, 65mm, 70mm, 75mm, 80mm, 85mm, 90mm, 95mm, 100mm, 120m m, 150mm or 200mm, or approximately 10mm, 11mm, 12mm, 13mm , 14mm, 15mm, 17mm, 20mm, 25mm, 30mm, 35mm, 40mm , 45mm, 50mm, 60mm, 65mm, 70mm, 75mm, 80mm, 85mm , 90mm, 95mm, 100mm, 120mm, 150mm or 200mm, also They are spaced apart by any range of values ​​between them. In some embodiments, the through holes are The particles are distributed uniformly through the element on at least one surface of the element, or substantially uniformly. They are distributed uniformly. In some embodiments, the elements are 0.1% and 0.5% of the total element volume. %, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 8%, 10%, 15% , 20%, 25%, 30% or 40%, approximately 0.1%, 0.5%, 1%, 1.5%, 2 %, 2.5%, 3%, 4%, 5%, 6%, 8%, 10%, 15%, 20%, 25%, 30 % or 40%, at least 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 8%, 10%, 15%, 20%, 25%, 30%, or 40% %, or at least about 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 8%, 10%, 15%, 20%, 25%, 30%, or 40%, or through holes of any range of values ​​between them. In some embodiments, a self-supporting element The base does not include through holes.

[0048] In some embodiments, adjacent pairs of freestanding precursor elements are 1, 2, 3, 4, 5 , 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 2 0, 25, 30 or 50 channels, or approximately 1, 2, 3, 4, 5, 6, 7, 8, 9 , 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30 as well Or include channels with values ​​of 50 or any range between them. In this embodiment, each of the multiple channels has a characteristic dimension when viewed from outside the element stack. (For example, length, width, diameter) 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm m, 8mm, 9mm, 10mm, 11mm, 12mm, 13mm, 14mm, 15mm, 17mm, 20mm, 25mm, 30mm, 35mm, 40mm, 45mm, 50mm, 60mm, 70mm, 75mm or 100mm, or approximately 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, 10mm, 11mm, 12mm, 1 3mm, 14mm, 15mm, 17mm, 20mm, 25mm, 30mm, 35mm, 4 0mm, 45mm, 50mm, 60mm, 70mm, 75mm or 100mm, is any range of values ​​between them. In some embodiments, each of the multiple channels From another channel, 10mm, 11mm, 12mm, 13mm, 14mm, 15mm , 17mm, 20mm, 25mm, 30mm, 35mm, 40mm, 45mm, 50mm , 60mm, 65mm, 70mm, 75mm, 80mm, 85mm, 90mm, 95mm 100mm, 120mm, 150mm or 200mm, or approximately 10mm, 11m m, 12mm, 13mm, 14mm, 15mm, 17mm, 20mm, 25mm, 30m m, 35mm, 40mm, 45mm, 50mm, 60mm, 65mm, 70mm, 75m m, 80mm, 85mm, 90mm, 95mm, 100mm, 120mm, 150mm also They are spaced apart by a value of 200 mm, or any range in between. In the configuration, at least one of the multiple channels is an adjacent pair of independent elements. Extend the length. In some embodiments, each of the multiple channels is an adjacent pair of self It extends along the length of the upright element. In some embodiments, the freestanding precursor element is Does not include through holes.

[0049] In some embodiments, the freestanding precursor elements are 0.5 mm, 1 mm, 2 mm, and 3 mm in size. m, 4mm, 5mm, 6mm, 8mm, 10mm, 20mm, 40mm, 60mm or The lengths are 100mm, approximately 0.5mm, 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, and 8mm. m, 10mm, 20mm, 40mm, 60mm or 100mm, up to a maximum of 0.5mm. 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 8mm, 10mm, 20mm, 40 mm, 60mm or 100mm, or up to approximately 0.5mm, 1mm, 2mm, 3m m, 4mm, 5mm, 6mm, 8mm, 10mm, 20mm, 40mm, 60mm or It has a thickness of 100 mm, or any value in between.

[0050] In some embodiments, the freestanding precursor element is 1 g / cm³ 3 , 1.2 g / cm³ 3 , 1 0.3g / cm³ 3 1.4 g / cm³ 3 1.5 g / cm³ 3 1.6 g / cm³ 3 1.7 g / cm³ 3 1.8 g / cm³ 3 1.9 g / cm³ 3 , 2g / cm³ 3 , 2.2 g / cm³ 3 , 2.3g / c m 3 2.4 g / cm³ 3 2.6 g / cm³ 3 2.8 g / cm³ 3 , 3g / cm³ 3 3.5g / cm 3 , 4g / cm³ 3 4.5 g / cm³ 3 Or 5g / cm³ 3 , or approximately 1 g / cm³ 3 , 1 0.2g / cm³ 3 1.3 g / cm³ 3 1.4 g / cm³ 3 1.5 g / cm³ 3 1.6 g / cm³ 3 1.7 g / cm³3 1.8 g / cm³ 3 1.9 g / cm³ 3 , 2g / cm³ 3 , 2.2g / c m 3 2.3 g / cm³ 3 2.4 g / cm³ 3 2.6 g / cm³ 3 2.8 g / cm³ 3 , 3g / cm 3 3.5 g / cm³ 3 , 4g / cm³ 3 4.5 g / cm³ 3 Or 5g / cm³ 3 ,or This includes the density of values ​​within any range between them. In some embodiments, the density of elements is through This is the density of the material of the elements excluding the through-pores.

[0051] In some embodiments, the self-supporting firing element is 90% by weight, 91% by weight, 92% by weight , 93% by weight, 94% by weight, 95% by weight, 96% by weight, 97% by weight, 98% by weight, 99% by weight Volume%, 99.2% by weight, 99.5% by weight, 99.8% by weight, 99.9% by weight, or 10 0 wt% cathode active material, approximately 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt% Weight%, 95% by weight, 96% by weight, 97% by weight, 98% by weight, 99% by weight, 99.2% by weight Cathodes of %, 99.5% by weight, 99.8% by weight, 99.9% by weight, or 100% by weight Active material, at least 90% by weight, 91% by weight, 92% by weight, 93% by weight, 94% by weight, 9 5% by weight, 96% by weight, 97% by weight, 98% by weight, 99% by weight, 99.2% by weight, 99. 5% by weight, 99.8% by weight, 99.9% by weight, or 100% by weight of cathode active material, or at least about 90% by weight, 91% by weight, 92% by weight, 93% by weight, 94% by weight, 95% by weight Weight%, 96% by weight, 97% by weight, 98% by weight, 99% by weight, 99.2% by weight, 99.5 Cathode active material in weight %, 99.8% by weight, 99.9% by weight, or 100% by weight, This includes cathode active material of any range of values ​​between them. In some embodiments, the cathode The cathode active material comprises crystalline cathode active material particles. In some embodiments, self-contained firing Components are 50% by weight, 60% by weight, 70% by weight, 80% by weight, 90% by weight, 95% by weight , 98% by weight, 99% by weight, or 100% by weight crystalline cathode active material particles, approximately 50 units Amount%, 60% by weight, 70% by weight, 80% by weight, 90% by weight, 95% by weight, 98% by weight, 9 9% by weight or 100% by weight of crystalline cathode active material particles, at least 50% by weight, 6 0% by weight, 70% by weight, 80% by weight, 90% by weight, 95% by weight, 98% by weight, 99% by weight Alternatively, 100% by weight of crystalline cathode active material particles, or at least about 50% by weight of 6 0% by weight, 70% by weight, 80% by weight, 90% by weight, 95% by weight, 98% by weight, 99% by weight Alternatively, 100% by weight of crystalline cathode active material particles, or any range of values ​​between them. It contains crystalline cathode active material particles. In some embodiments, the cathode active material is lithium Um-nickel-manganese-cobalt oxide (NMC), lithium-manganese oxide (LMO), Lithium iron phosphate (LFP), lithium cobalt oxide (LCO), lithium titanate ( LTO, lithium nickel manganese oxide (LNMO), lithium nickel cobalt Luminium oxide (NCA), nickel-manganese aluminum oxide (NMA), nickel Aluminum cobalt manganese oxide (NMCA), LiNiO2, or combinations thereof. Selected from the combinations.

[0052] In some embodiments, the freestanding firing elements are 5% by weight, 4% by weight, 3% by weight, and double-layered. Lithium reagent in 1% by weight, 1% by weight, 0.5% by weight, or 0.1% by weight, approximately 5% by weight, 4 units Lithium test in 1% by weight, 3% by weight, 2% by weight, 1% by weight, 0.5% by weight, or 0.1% by weight Drugs, up to 5% by weight, 4% by weight, 3% by weight, 2% by weight, 1% by weight, 0.5% by weight or 0.1% by weight lithium reagent, or up to approximately 5% by weight, 4% by weight, 3% by weight, 2% by weight , 1% by weight, 0.5% by weight, or 0.1% by weight of lithium reagent, or any amount in between. It contains a lithium reagent within a specified range of values. In some embodiments, the freestanding firing element is 5 Weight %, 4% by weight, 3% by weight, 2% by weight, 1% by weight, 0.5% by weight, or 0.1% by weight Metal precursors, approximately 5% by weight, 4% by weight, 3% by weight, 2% by weight, 1% by weight, and 0.5% by weight. Alternatively, 0.1 wt% of the metal precursor, up to 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 A metal precursor in weight %, 0.5 weight %, or 0.1 weight %, or up to approximately 5 weight %, 4 Metallic precursors in weight %, 3% by weight, 2% by weight, 1% by weight, 0.5% by weight, or 0.1% by weight. The material comprises a metal precursor in a body or any range of values ​​between them. In some embodiments, The self-supporting firing elements are water-free or substantially water-free. In some embodiments... The self-contained firing elements are 1% by weight, 0.5% by weight, 0.1% by weight, or 0.01% by weight. % water, approximately 1% by weight, 0.5% by weight, 0.1% by weight or 0.01% by weight of water, up to 1% by weight, 0.5% by weight, 0.1% by weight, or 0.01% by weight of water, or up to approximately 1 Water by weight %, 0.5% by weight, 0.1% by weight, or 0.01% by weight, or in between. It contains water in any range of values. In some embodiments, the freestanding firing element is 0.01 Weight%, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.2% by weight, 1.5% by weight, or 2% by weight binder, approximately 0.01% by weight, 0.0 5% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.2% by weight, 1.5% or 2% by weight binder, up to 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight %, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.2% by weight, 1.5% by weight A binder of % or 2% by weight, or up to approximately 0.01% by weight, 0.05% by weight, 0 .1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight , 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.2% by weight, 1.5% by weight Alternatively, it may include a binder of 2% by weight, or a binder of any range of values ​​between those two weights. In some embodiments, the freestanding firing element does not contain a binder, or is substantially free of one. Not included in the target. In some embodiments, the self-supporting firing element is the decomposed binder residue. Contains residue. In some embodiments, the self-standing firing element is decomposed binder residue. Not included, or substantially not included. In some embodiments, the freestanding firing element is 10% by weight, 9% by weight, 8% by weight, 7% by weight, 6% by weight, 5% by weight, 4% by weight, 3% by weight , 2% by weight, 1% by weight, 0.5% by weight, or 0.1% by weight of residual lithium, approximately 10g %, 9% by weight, 8% by weight, 7% by weight, 6% by weight, 5% by weight, 4% by weight, 3% by weight, 2% by weight % or 1% by weight residual lithium, up to 10% by weight, 9% by weight, 8% by weight, 7% by weight , 6% by weight, 5% by weight, 4% by weight, 3% by weight, 2% by weight, or 1% by weight residual lithium , or up to approximately 10% by weight, 9% by weight, 8% by weight, 7% by weight, 6% by weight, 5% by weight, 4 Residual lithium of % by weight, 3% by weight, 2% by weight, or 1% by weight, or any in between. Includes residual lithium within the range of values.

[0053] In some embodiments, the self-supporting firing element includes multiple through holes. In terms of form, freestanding fired elements, when stacked, have less space between adjacent elements. It also includes a surface pattern in which another channel is formed. In some embodiments, Multiple through-holes and / or channels in the upright firing element are retained from the freestanding precursor element. They are either made to be or substantially held. In some embodiments, the freestanding firing element is 2, 4, 6, 8, 10, 12, 15, 20, 25, 30 or 50 through holes, or approximately , 2, 4, 6, 8, 10, 12, 15, 20, 25, 30 or 50 through holes, Includes through holes of any range of values ​​between them. In some embodiments, multiple through holes Each has a diameter of 1mm, 5mm, 10mm, 15mm, 20mm, 25mm, and 30mm. 40mm, 50mm, 75mm, or 100mm, or approximately 1mm, 5mm, or 10mm , 15mm, 20mm, 25mm, 30mm, 40mm, 50mm, 75mm or 1 00 mm, or any value within that range. In some embodiments, multiple Each through-hole is 10mm, 11mm, 12mm, 13mm, and 14mm from the other through-holes. , 15mm, 17mm, 20mm, 25mm, 30mm, 35mm, 40mm, 45mm , 50mm, 60mm, 65mm, 70mm, 75mm, 80mm, 85mm, 90mm 95mm, 100mm, 120mm, 150mm or 200mm, or approximately 10m m, 11mm, 12mm, 13mm, 14mm, 15mm, 17mm, 20mm, 25m m, 30mm, 35mm, 40mm, 45mm, 50mm, 60mm, 65mm, 70m m, 75mm, 80mm, 85mm, 90mm, 95mm, 100mm, 120mm, 1 They are spaced 50mm or 200mm apart, or any value in between. In some embodiments, the through-holes are uniformly distributed through the element on at least one surface of the element. They are distributed or substantially uniformly distributed. In some embodiments, the elements are , 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4% of the total element volume, 5%, 6%, 8%, 10%, 15%, 20%, 25%, or 30% through holes, approximately 0.1 %, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 8%, 10 %, 15%, 20%, 25%, or 30% through holes, at least 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 8%, 10%, 15%, 2 0%, 25%, or 30% through holes, or at least approximately 0.1%, 0.5%, or 1%. 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 8%, 10%, 15%, 20%, This includes through holes with a 25% or 30% penetration rate, or any range of values ​​in between. In some embodiments, the self-supporting firing element does not include through holes.

[0054] In some embodiments, adjacent pairs of freestanding firing elements are 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 25, 30 or 50 channels, or approximately 1, 2, 3, 4, 5, 6, 7, 8, 9 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30 if This includes channels with 50 or any range of values ​​between them. In this embodiment, each of the multiple channels has a characteristic dimension when viewed from outside the element stack ( For example, the length, width, and diameter are 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, and 7mm. , 8mm, 9mm, 10mm, 11mm, 12mm, 13mm, 14mm, 15mm, 1 7mm, 20mm, 25mm, 30mm, 35mm, 40mm, 45mm, 50mm, 6 0mm, 70mm, 75mm or 100mm, or approximately 1mm, 2mm, 3mm, 4 mm, 5mm, 6mm, 7mm, 8mm, 9mm, 10mm, 11mm, 12mm, 13 mm, 14mm, 15mm, 17mm, 20mm, 25mm, 30mm, 35mm, 40 mm, 45mm, 50mm, 60mm, 70mm, 75mm or 100mm, or It is any range of values ​​between them. In some embodiments, each of the multiple channels is , from another channel, 10mm, 11mm, 12mm, 13mm, 14mm, 15mm, 17mm, 20mm, 25mm, 30mm, 35mm, 40mm, 45mm, 50mm, 60mm, 65mm, 70mm, 75mm, 80mm, 85mm, 90mm, 95mm, 100mm, 120mm, 150mm, or 200mm, or approximately 10mm, 11mm , 12mm, 13mm, 14mm, 15mm, 17mm, 20mm, 25mm, 30mm , 35mm, 40mm, 45mm, 50mm, 60mm, 65mm, 70mm, 75mm , 80mm, 85mm, 90mm, 95mm, 100mm, 120mm, 150mm if They are spaced 200 mm apart, or any value in between. In terms of morphology, at least one of the multiple channels is the length of a pair of adjacent independent elements. To extend the distance. In some embodiments, each of the multiple channels is an adjacent pair of independent It extends over the length of the element. In some embodiments, the freestanding precursor element penetrates It does not include through-pores.

[0055] In some embodiments, the freestanding firing elements are 0.5 mm, 1 mm, 2 mm, and 3 mm in size. , 4mm, 5mm, 6mm, 8mm, 10mm, 20mm, 40mm, 60mm or 100mm, approx. 0.5mm, 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 8mm , 10mm, 20mm, 40mm, 60mm or 100mm, up to 0.5mm, 1 mm, 2mm, 3mm, 4mm, 5mm, 6mm, 8mm, 10mm, 20mm, 40m m, 60mm or 100mm, or up to approximately 0.5mm, 1mm, 2mm, or 3mm , 4mm, 5mm, 6mm, 8mm, 10mm, 20mm, 40mm, 60mm or It has a thickness of 100 mm, or any range of values ​​in between.

[0056] In some embodiments, the self-supporting firing element is 0.8 g / cm³. 3 , 0.9 g / cm³ 3 , 1 g / cm³ 3 , 1.2 g / cm³ 3 1.3 g / cm³ 3 1.4 g / cm³ 3 1.5 g / cm³ 3 , 1.6 g / cm 3 , 1.7 g / cm 3 , 1.75 g / cm 3 , 1.8 g / cm 3 , 1.9 g / cm 3 , 2 g / cm 3 , 2.2 g / cm 3 , 2.3 g / cm 3 , 2.4 g / cm 3 , 2.6 g / cm 3 , 2.8 g / cm 3 , 3 g / cm[[ID=*28]] 3 , 3.5 g / cm 3 , 4 g / cm 3 , 4.5 g / cm 3 , 5 g / cm 3 , 5.5 g / cm 3 or 6 g / cm 3 , or approximately 0.8 g / cm 3 , 0.9 g / cm 3 , 1 g / cm 3 , 1.2 g / cm 3 , 1.3 g / cm 3 , 1.4 g / c m 3 , 1.5 g / cm 3 , 1.6 g / cm 3 , 1.7 g / cm 3 , 1.75 g / cm 3 , 1. 8 g / cm 3 , 1.9 g / cm 3 , 2 g / cm 3 , 2.2 g / cm 3 , 2.3 g / cm 3 , 2 .4 g / cm 3 , 2.6 g / cm 3 , 2.8 g / cm​​​​​​​​​​​​​​​​ or include the density of values ​​within any range between them. In some embodiments, self-contained burning The constituent elements are free from or substantially free from cracks.

[0057] In some embodiments, the freestanding precursor elements form freestanding prebaked elements. Preheating of the element If the precursor is not pre-oxidized, this involves dehydration of free water and conversion of LiOH·H2O to LiOH. Decomposition of and / or metal hydroxide precursors (e.g., Ni 0.83 Mn 0.06 Co 0.11 (OH 2) Metal oxide precursors (e.g., Ni 0.83 Mn 0.06 Co 0.11 Helps decompose into O) This is possible. In some embodiments, the self-supporting pre-baked element is a precursor and / or As explained regarding the firing element, when stacked, it has at least one channel It may include through holes and surface patterns that enable... The pre-baked elements are similar to those described for the precursor and / or baked elements. These may include other similar properties (e.g., dimensions, density, and / or chemical composition). Element and cathode active material formation step

[0058] Figure 4 shows an example of cathode material formation through a formation process according to several embodiments. The flowchart shown is 400. Reagent 402 and precursor 404 are provided, and the mixture 40 6. A mixture is formed. Examples of reagent 402 include LiCO3, LiOH, and L Examples of precursors include iOH·H2O, and metal oxides (MO) n ), metal hydroxide (M(OH) n ), and metal carbonates (M(CO3) n ) are examples. Mixing step 40 After the mixture is formed in step 6, this mixture is used for element fabrication and stacking steps. In step 408, precursor elements are formed on a plate or substrate. Then, The elements are heated in the firing step 410 to form the fired elements. The fired elements are removed from the substrate. The element is then destroyed and fired in plate flip and size reduction step 412. The powder is formed, the substrate is inspected, and in plate return and inspection step 414 The element fabrication and stacking step 408 is returned. The calcined element powder is then treated in the surface treatment step 4. At 16, the surface is treated to form the cathode active material LiMeO2418.

[0059] In some embodiments, the process involves mixing a reagent with a metal precursor to form a precursor mixture. This includes performing the following. In some embodiments, the process involves compressing a precursor mixture to create a precursor This includes making it a body element. In some embodiments, the process involves heating the precursor element , including forming a calcined element containing a cathode active material. In some embodiments, a precursor Body elements and / or fired elements are freestanding elements.

[0060] In some embodiments, the process involves modifying the precursor element to include through holes. Includes. In some embodiments, the precursor element is supported by the substrate while being heated. ru.

[0061] In some embodiments, the precursor element is a tunnel kiln (e.g., low temperature and / or It is transported through a high-temperature tunnel kiln. In some embodiments, the precursor or p The rebake elements are heated in a high-temperature tunnel kiln. In some embodiments, the low-temperature A high-temperature kiln is the same kiln set to different temperatures. In some embodiments, Low-temperature kilns and high-temperature kilns are different kilns. In some embodiments, heating is performed. Oxidizing atmosphere (for example, an atmosphere containing oxygen, such as air or an oxygen-rich atmosphere) (e.g., oxygen exceeding 21% by volume, exceeding 23.5% by volume, or exceeding 25% by volume), inert atmosphere (e.g.) For example, helium, neon, argon, krypton, xenon, radon, and / or nitrogen (Atmosphere containing elements) or reducing atmosphere (e.g., hydrogen, carbon monoxide, and / or sulfide) This is carried out in a hydrogen-containing atmosphere. For example, in some embodiments, lithium iron phosphate (LFP) formation occurs by heating (e.g., calcination) in an inert or reducing atmosphere. This is done. In some embodiments, during the pre-baking and / or firing heating of the elements, The gas passes through the through holes and / or channels. In some embodiments, the gas oxidizes Gas (e.g., air or an oxygen-rich atmosphere containing oxygen), inert gas, or reflux Includes source gas. In some embodiments, heating is performed at 700°C, 725°C, 750°C, 76°C. 0℃, 780℃, 800℃, 820℃, 840℃, 850℃, 860℃, 880℃, 90 0°C, 950°C or 1000°C, approximately 700°C, 725°C, 750°C, 760°C, 78 0℃, 800℃, 820℃, 840℃, 850℃, 860℃, 880℃, 900℃, 95 0°C or 1000°C, at least 700°C, 725°C, 750°C, 760°C, 780°C °C, 800°C, 820°C, 840°C, 850°C, 860°C, 880°C, 900°C, 950°C °C or 1000°C, or at least about 700°C, 725°C, 750°C, 760°C, 780℃, 800℃, 820℃, 840℃, 850℃, 860℃, 880℃, 900℃, The process is carried out at a temperature of 950°C, 1000°C, or any value within that range. In some embodiments, the process includes preheating a self-supporting precursor element.

[0062] In some embodiments, the precursor element is cooled during the pre-baking or preheating step. The pre-baked elements (e.g., bricks and tiles) are heated in a tunnel kiln. In some embodiments, the pre-baking step is performed before the firing heating of the elements. In some embodiments, the firing and heating of the elements further includes a pre-baking step. In some embodiments, preheating is performed at a temperature lower than the firing temperature. In this embodiment, heating is performed at 80°C, 100°C, 120°C, 140°C, 160°C, and 180°C. 200℃, 220℃, 230℃, 240℃, 250℃, 260℃, 280℃, 300℃ 320℃, 350℃, 400℃, 450℃, 500℃, 550℃, 600℃, 650℃ 700℃ or 750℃, approximately 80℃, 100℃, 120℃, 140℃, 160℃, 1 80℃, 200℃, 220℃, 230℃, 240℃, 250℃, 260℃, 280℃, 3 00℃, 320℃, 350℃, 400℃, 450℃, 500℃, 550℃, 600℃, 6 50°C, 700°C or 750°C, or at least 80°C, 100°C, 120°C, 140°C 160℃, 180℃, 200℃, 220℃, 230℃, 240℃, 250℃, 260℃ 280℃, 300℃, 320℃, 350℃, 400℃, 450℃, 500℃, 550℃ , 600℃, 650℃, 700℃ or 750℃, at least about 80℃, 100℃, 1 20℃, 140℃, 160℃, 180℃, 200℃, 220℃, 230℃, 240℃, 2 50℃, 260℃, 280℃, 300℃, 320℃, 350℃, 400℃, 450℃, 5 00°C, 550°C, 600°C, 650°C, 700°C or 750°C, or any of those. The process is carried out at a temperature within any range of values ​​between the two. In some embodiments, the process is carried out at the cathode It does not involve an additional heating step of the active material. In some embodiments, the element pre-baking is During firing and / or heating, gas passes through through holes and / or channels. In some embodiments, the gas contains oxygen (e.g., air). In some embodiments, a self-supporting The pre-baked and / or fired elements are free from cracks, or substantially free from cracks. In some embodiments, heating (e.g., pre-baking and / or baking) is performed on the precursor. Decompose the binder in the element and / or pre-baked element (e.g., burn and / or Carbonization occurs. In some embodiments, the decomposed binder residue is used to pre-bake elements. It is vaporized from the and / or firing element. In some embodiments, the decomposed binder At least a portion of the residue (e.g., a measurable amount) is used in the pre-baked elements and / or firing process. It remains in the element. In some embodiments, the pre-baked and / or fired elements decompose. It does not contain, or substantially does not contain, any binder residue. In some embodiments, Heating reduces the density of the elements.

[0063] In some embodiments, the process involves destroying the freestanding calcined elements to form calcined element powder. This includes performing actions. In some embodiments, destruction includes crushing, grinding, and combining those actions. including steps selected from the combination. In some embodiments, the process includes a cathode processing the active material. In some embodiments, the processing includes screening, washing, filtering, drying, coating, and steps selected from combinations thereof. In some embodiments, the coating includes coating the cathode active material with a coating compound selected from TiO2, Al2O3, and combinations thereof. In some embodiments, the coating is performed by a method selected from spray coating, mechanical fusion, and combinations thereof.

[0064] Figures 5A to 5D show images of various bricks with through holes at various stages of the forming process according to some embodiments. Figure 5A shows the pressed precursor brick, Figure 5B shows the pre-baked brick. Figure 5C shows the fired brick that maintained its form through the firing process, and Figure 5D shows the fired brick that did not maintain its form through the firing process and shows cracks and fissures. Figures 6A and 6B show images of stacked fired tiles that maintained their form through the firing process and stacked tiles that did not maintain their form through the firing process, respectively. respectively. through the firing process, and Figure 5D shows the fired brick that did not maintain its form through the firing process and shows cracks and fissures. Figures 6A and 6B show images of stacked fired tiles that maintained their form through the firing process and stacked tiles that did not maintain their form through the firing process, respectively. Energy storage device

[0065] Once the cathode active material is isolated, it can be used to prepare an electrode for an energy storage device. In some embodiments, the electrode film includes the cathode active material described herein. In some embodiments, the cathode active material is incorporated into the electrode film. In some embodiments, the electrode film further includes a binder. In some embodiments, the electrode film...​​ It includes a current collector and the electrode film described in this specification. In some embodiments, the electrode film is disposed on the current collector to form a cathode electrode.

[0066] In some embodiments, the energy storage device utilizes the cathode active material described in this specification. In some embodiments, the energy storage device includes a separator, an anode electrode , the cathode electrode described in this specification, and a housing. The separator, the anode electrode and the cathode electrode are disposed within the housing, and the separator is disposed between the anode electrode and the cathode electrode. In some embodiments, the energy storage device is formed by disposing a separator, an anode electrode, and the cathode electrode described in this specification within a housing, and the separator is disposed between the anode electrode and the cathode electrode. In some embodiments, the energy storage device is a battery. In some embodiments, the energy storage device is a lithium-ion battery. In some embodiments, the energy storage device is a battery. In some embodiments, the energy storage device is a lithium-ion battery.

Examples

[0067] Exemplary embodiments of the present disclosure, including processes, materials, and / or resulting products, are described in the following examples. Exemplary embodiments of the present disclosure, including processes, materials, and / or resulting products, are described in the following examples. Example 1 <C

[0068] Micron-sized powder of lithium carbonate and electrolytic manganese dioxide (EMD) were mixed at a molar ratio of Li / Mn = 1.05, and then compressed into self-standing green bricks having a density of 1.8 g / cm and dimensions of 100 mm (H) × 150 mm (W) × 300 mm 3 (L). Then, the green bricks were stacked on a ceramic plate and placed in a kiln, and fired in air at 850 It was fired at °C for 18 hours. After cooling, the self-standing fired bricks were crushed and ground into powder, and then... After that, it is sieved with a 400-mesh filter and used as a cathode material for lithium-ion batteries. The final product obtained was LiMn2O4(LMO). Example 2

[0069] Ni 0.5 Mn 0.3 Co 0.3 (OH)2 spherical powder is pre-baked at 500°C for 2 hours and Ni 0.5 Mn 0.3 Co 0.3 After obtaining O (dehydration precursor), lithium carbonate is prepared with a molar ratio of Li / Mn = 1.08. It was mixed with M. To improve the integrity of the bricks, 15% by weight of water was added at the end of the mixing step. It was added to the mixture. Then the mixture was placed in a 100mm(H)×150mm(W)×300m 2.5 g / cm² in m(L) dimensions 3 It was compressed into freestanding, unprocessed bricks having the following density. Then, the unprocessed bricks are stacked on a ceramic plate and placed in the kiln, and air is introduced. The bricks were fired at 880°C for 12 hours. After cooling, the self-supporting fired bricks were crushed and ground into powder. Next, it is sieved with a 400-mesh sieve to form layered NMC532 for lithium-ion batteries. The final product of the sword material was obtained. Example 3

[0070] Lithium carbonate and Ni 0.6 Mn 0.2 Co 0.2 CO3 was mixed with Li / Mn at a molar ratio of 1.06. At the end of the mixing step, 2% by weight of water was added to the mixture. Then the mixture was 30 Dimensions: 0mm (L) x 50mm (W) x 150mm (H), weight: 2.2g / cm³ 3 The density Compressed into self - standing green bricks. Then, the green bricks were stacked on a ceramic plate and fired at 850 °C for 12 hours while flowing dry air after being put into a kiln. After cooling , the self - standing fired bricks were crushed, ground into powder, and then sieved through a 400 - mesh screen to obtain the final product of the layered NMC622 cathode material for lithium - ion batteries. Example 4

[0071] Lithium hydroxide monohydrate and Ni 0.6 Mn<00001...Co 0.2 (OH)2 were mixed together at a molar ratio of Li / Mn = 1.0 :6, and a 4 wt% aqueous solution was added to the mixture at the end of the mixing step, where the aqueous solution contains 5 wt% polyvinyl alcohol (PAV). Then, the mixture was compressed into self - standing green bricks with a density of 2.0 g / cm³ and dimensions of 100 mm (H)×150 mm (W)×300 mm (L). Twelve cylindrical through - holes (diameter = 20 mm) were uniformly distributed along the longitudinal direction inside the bricks. Then, the green bricks were stacked on a ceramic 3 plate and fired at 850 °C for 12 hours while flowing dry air after being put into a kiln. After cooling, the self - standing fired bricks were crushed, ground into powder, and then sieved through a 400 - mesh screen to obtain the final product of the layered NMC622 cathode material for lithium - ion batteries. screen to obtain the final product of the layered NMC622 cathode material for lithium - ion batteries. Example 5

[0072] Lithium hydroxide monohydrate and Ni 0.8 Mn 0.1 Co 0.1 (OH)2 were mixed together at a molar ratio of Li / Mn = 1.0 :2, and a 4 wt% aqueous solution was added to the mixture until the end of the mixing step ​​​And here, the aqueous solution contains 2% by weight of sodium carboxymethylcellulose (CMC). Including the mixture, then measure the dimensions of 100mm (H) x 150mm (W) x 300mm (L). The law stipulates 2.5 g / cm³ 3 It is compressed into a freestanding, unprocessed brick, with 12 squares inside the brick. The through holes (side length = 20 mm) were uniformly distributed along the length direction. Next, the unprocessed The munga are stacked on a ceramic plate, placed in the kiln, and heated to 780°C while oxygen is flowing through. It was fired for 12 hours. After cooling, the self-supporting fired bricks were crushed and ground into powder, then 40 It is sieved with a 0 mesh, then subjected to a surface treatment process including washing, filtration, and drying, and Next, it was passed through a mechanical fusion machine and coated with 0.5 wt% nano-sized TiO2. Example 6

[0073] Lithium hydroxide and Ni 0.8 Co 0.1 Al 0.1 (OH)2 and Li / Mn in a molar ratio of 1.02 Mixed. Then, the powder was placed in a container measuring 100mm(H) x 150mm(W) x 300mm(L). Dimensions: 1.8 g / cm 3 It was compressed into freestanding, unprocessed bricks. Then the unprocessed bricks were set The plates are stacked on a lamin plate, placed in the kiln, and heated to 760°C for 12 hours while oxygen is flowing through. The bricks were fired. After cooling, the bricks were crushed, ground into powder, and then sieved through a 400-mesh sieve. Then, it is subjected to a surface treatment process including washing, filtering, and drying, and subsequently passed through a mechanical fusion machine. It was then coated with 0.3 wt% nano-sized Al2O3. Example 7

[0074] LiOH·H2O, Ni 0.83 Mn 0.06 Co 0.11 (OH)2, as a binder additive Prepare a mixture of thorium carboxymethylcellulose (CMC) and water, and apply it to the tiles. Compressed. LiOH·H2O and Ni 0.83 Mn 0.06 Co 0.11 The molar ratio with (OH)2 is 1.05 The weight was 5. The weight of the CMC additive was LiOH·H2O and Ni 0.83 Mn 0.06 Co 0.11 (O It is 0.25% of the total weight with H2, and the weight of water is LiOH·H2O and Ni 0.83 Mn 0.06 C o 0.11 It accounted for 7.0% of the total weight with (OH)2.

[0075] To prepare the tiles, LiOH·H2O, Ni 0.83 Mn 0.06 Co 0.11 (OH)2 oyo The CMC mixture was dry-mixed, and then water was added during mixing. The wet mixture was then filled into the mold. The tiles were filled in and then pressed into the designed geometric shapes. The thickness of the material is 10-50 mm, and the bulk density is 2.20 g / cm³. 3 That was the case.

[0076] These precursor tiles are self-supporting, and six precursor tiles are stacked to form a 250°C structure. The dough was placed in the kiln while hot air was blown through it, and pre-baking was performed. After pre-baking, it was self-supporting. The pre-baked tiles are then placed into a roller hearth kiln (RHK) in a controlled atmosphere. The tiles were fired. Then, the freestanding fired tiles were crushed, pulverized, filtered, washed, and dried. Then, the active material was isolated.

[0077] Such mixtures remain self-supporting when stacked, pre-baked, and fired. It was demonstrated that a self-supporting precursor tile could be achieved. Comparative Example

[0078] LiOH·H2O, Ni 0.83 Mn 0.06 Co 0.11 (OH)2, as a binder additive Prepare a mixture of thorium carboxymethylcellulose (CMC) and water, and apply it to the tiles. Compressed. LiOH·H2O and Ni 0.83 Mn 0.06 Co 0.11 The molar ratio with (OH)2 is 1.03 The weight was 0. The weight of the CMC additive was LiOH·H2O and Ni 0.83 Mn 0.06 Co 0.11 (O It is 0.05% of the total weight with H2, and the weight of water is LiOH·H2O and Ni 0.83 Mn 0.06 C o 0.11 It accounted for 3.0% of the total weight with (OH)2.

[0079] To prepare the tiles, LiOH·H2O, Ni 0.83 Mn 0.06 Co 0.11 (OH)2 oyo The CMC mixture was dry-mixed, and then water was added during mixing. The wet mixture was then filled into the mold. The tiles were filled in and then pressed into the designed geometric shapes. The thickness of the material is 10-50 mm, and the bulk density is 1.90 g / cm³. 3 That is the case.

[0080] Such mixtures remain self-supporting when stacked, pre-baked, and fired. It was demonstrated that a precursor tile, not a precursor tile, could be achieved.

[0081] Although specific embodiments have been described, these embodiments are presented as examples only, and this publication... This is not intended to limit the scope of the indications. In fact, the novel methods and the The stem can be embodied in various other forms. Furthermore, without departing from the spirit of this disclosure , making various omissions, substitutions and modifications in the systems and methods described herein. This is possible. The attached claims and their equivalents are not included in the scope and spirit of this disclosure. It is intended to encompass forms or modifications that may occur.

[0082] Features, materials, properties, or examples described in relation to a particular aspect, embodiment, or example The group shall not be any of the terms and conditions set forth in this section or elsewhere in this specification, unless otherwise specified. This specification should be understood to be applicable to other aspects, embodiments, or examples of this specification. All of the features disclosed in this document (including the attached claims, abstract, and drawings), and and / or any method or step of process disclosed in that manner A combination in which at least some of the features and / or steps are mutually exclusive. Except for the combinations mentioned above, any combination is possible. Protection is any of the aforementioned actual The protection is not limited to the details of the application. The protection is as specified herein (appendix to the claims, abstract, and Any novel features or any novel combination of features disclosed in (including drawings), or any novelty of any method or step of process disclosed in that manner , or any new combination.

[0083] Furthermore, certain features described in this disclosure in the context of separate implementation forms may be considered in a single implementation form It can also be implemented in combination in a given state. Conversely, it can be explained in the context of a single implementation form. The various features present in multiple implementations are either separate or in any appropriate partial combination. It can also be implemented in combination. Furthermore, the features are those that act in specific combinations. It may be stated, however, that one or more features from the claimed combination may, in some cases Then, it can be removed from the combination, and this combination becomes a partial combination or It can be claimed as a variation of a partial combination.

[0084] Furthermore, the operation may be shown in the drawings or described herein in a specific order, but Such actions, in order to achieve the desired result, are performed in a specific sequence or sequence as indicated. The actions do not need to be performed in any particular order, or not all actions need to be performed. Other behaviors not described may be incorporated into the exemplary methods and processes. For example, one or more actions before, after, simultaneously with, or in between any of the actions described. It is possible to perform additional actions. Furthermore, the actions can be rearranged in other implementations. The order can be changed. In some embodiments, the illustrations and / or open diagrams are shown. The actual steps taken in the process shown may differ from those shown in the diagram. Those skilled in the art will understand. Depending on the embodiment, certain steps among the steps described above You may remove it, or you may add other steps. Furthermore, the specific facts disclosed above The characteristics and attributes of the embodiment are combined in different ways to form additional embodiments. This is possible, and all of it is included within the scope of this disclosure. Furthermore, the implementation details in the above-mentioned forms The separation of various system components necessitates such separation in all implementation forms. It should not be understood as such; the components and systems described are generally considered to be a single product. Please understand that they may be integrated together or packaged into multiple products. For example, any of the components of the energy storage system described herein is energy They may be provided separately or integrated to form a storage system (e.g.) (For example, they are packaged together or attached together.)

[0085] For the purposes of this disclosure, specific aspects, advantages, and novel features are described herein. Not all such advantages can necessarily be achieved according to any particular embodiment. This is not the case. Therefore, for example, a person skilled in the art would know that this disclosure does not teach or suggest the same as described herein. Without necessarily achieving other possible advantages, one such advantage as taught herein They will recognize that it can be concretized or implemented to achieve the advantages or set of advantages.

[0086] Conditional language such as "can," "could," "might," or "may" Unless otherwise specified or understood to mean something else in the context in which it is used, generally In other words, a particular embodiment includes certain features, elements, and / or steps, but other embodiments The intention is to convey that it does not include voice. Therefore, such conditional language is Generally, features, elements, and / or steps are not included in one or more embodiments. It is required in the form of user input or program Whether or not these features, elements, and / or steps are any specific This necessarily includes logic for determining whether an embodiment should be included or performed. That does not mean...

[0087] Conjunctions such as the phrase "at least one of X, Y, and Z" are particularly clear. Unless otherwise stated, it is not possible to convey that items, terms, etc., could be X, Y, or Z. Therefore, such conjunctions are generally understood in the context in which they are commonly used. A defined embodiment is at least one of X, at least one of Y, and at least one of Z It is not intended to imply that its existence is necessary.

[0088] The terms "approximately," "about," "generally," and "substantially" used herein The degree of language used in the specification is still sufficient to perform the desired function or the desired conclusion. Represents a value, quantity, or characteristic close to the stated value, quantity, or characteristic that achieves the desired result.

[0089] The scope of this disclosure is limited by the specific disclosures of embodiments in this section or elsewhere in this specification. This is not intended to be limited to, and may be limited to, the information presented in this section or elsewhere in this specification. As such, or as may be presented in the future, the claims may be defined by the claims. The scope of the wording should be interpreted broadly based on the wording used in the claims. The examples described herein or, not limited to those in the course of application, these examples are not exclusive. This should be interpreted as follows.

[0090] Although specific embodiments have been described, these embodiments are presented as examples only, and this publication... This is not intended to limit the scope of the indications. In fact, the novel methods and the The stem can be embodied in various other forms. Furthermore, without departing from the spirit of this disclosure , making various omissions, substitutions and modifications in the systems and methods described herein. This is possible. The attached claims and their equivalents are not included in the scope and spirit of this disclosure. It is intended to encompass forms or modifications that may be found. Therefore, the scope of the present invention This is defined solely by reference to the attached claims.

Claims

1. A self-supporting firing element, It contains at least 95% by weight of cathode active material, The self-supporting firing element includes a corrugated upper surface and a corrugated lower surface configured to form a plurality of channels between adjacent self-supporting elements, each of the plurality of channels extending over the length of the pair of adjacent self-supporting elements, and each of the plurality of channels includes a first opening, a second opening, and a confined path positioned between the first and second openings. The aforementioned self-supporting firing element has a density of 1.7 to 2.3 g / cm³. The aforementioned corrugated upper surface is composed of multiple upper surface valleys, multiple upper surface peaks, radii of the upper surface valleys, depths of the upper surface valleys, and radii of the upper surface peaks. The corrugated lower surface is a self-supporting firing element composed of multiple lower valleys, multiple lower peaks, radii of the lower valleys, depth of the lower valleys, and radii of the lower peaks.

2. The self-supporting firing element according to claim 1, wherein the cathode active material comprises crystalline cathode active material particles.

3. The self-supporting firing element according to Claim 1, wherein the cathode active material is selected from the group consisting of lithium nickel manganese cobalt oxide (NMC), lithium manganese oxide (LMO), lithium iron phosphate (LFP), lithium cobalt oxide (LCO), lithium titanate (LTO), lithium nickel manganese oxide (LNMO), lithium nickel cobalt aluminum oxide (NCA), nickel manganese aluminum oxide (NMA), nickel cobalt manganese aluminum oxide (NMCA), LiNiO2, or combinations thereof.

4. The self-supporting firing element according to claim 1, wherein the self-supporting firing element contains a maximum of 1% by weight of residual lithium.

5. The self-supporting firing element according to claim 1, wherein the self-supporting firing element substantially contains no binder. component.

6. The self-supporting firing element according to claim 1, wherein the corrugated upper surface and the corrugated lower surface are continuous.

7. The self-supporting firing element according to any one of claims 1 to 6, wherein each channel has a channel width of 5 to 100 mm.

8. The self-supporting firing element according to any one of claims 1 to 6, wherein each channel has a channel spacing of 10 to 200 mm.

9. The self-supporting firing element according to any one of claims 1 to 6, wherein the self-supporting firing element has a density of 1.9 to 2.3 g / cm³.

10. The self-supporting firing element according to any one of claims 1 to 6, wherein the self-supporting firing element has a density of 1.7 to 1.8 g / cm³.

11. A process for preparing a cathode active material, The steps include mixing a solvent, a reagent, and a metal precursor to form a precursor mixture, A step of compressing the precursor mixture to form a self-supporting precursor element, wherein the self-supporting precursor element includes a corrugated upper surface and a corrugated lower surface configured to form a plurality of channels between adjacent self-supporting elements, each of the plurality of channels extending over the length of the pair of adjacent self-supporting elements, each of the plurality of channels including a first opening, a second opening, and a closed path positioned between the first and second openings, the corrugated upper surface being composed of a plurality of upper troughs, a plurality of upper peaks, radii of the upper troughs, depths of the upper troughs, and radii of the upper peaks, and the corrugated lower surface being composed of a plurality of lower troughs, a plurality of lower peaks, radii of the lower troughs, depths of the lower troughs, and radii of the lower peaks, A process comprising the steps of heating the self-supporting precursor element to form a self-supporting calcined element containing a cathode active material, wherein the self-supporting calcined element has a density of 1.7 to 2.3 g / cm³.

12. The process according to claim 11, wherein the reagent is a lithium reagent.

13. The process according to claim 12, wherein the lithium reagent is selected from the group consisting of lithium hydroxide, lithium hydroxide monohydrate, lithium carbonate, and combinations thereof.

14. The process according to claim 11, wherein the metal precursor is selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, and combinations thereof.

15. The process according to claim 11, wherein the metal precursor comprises a metal selected from the group consisting of Ni, Mn, Co, Al, Mg, Fe, Ti, and combinations thereof.

16. The process according to claim 11, wherein the solvent is water.

17. The process according to claim 11, wherein the precursor mixture comprises 0.1 to 20% by weight of a solvent.

18. The process according to any one of claims 11 to 17, wherein the precursor mixture further comprises a binder.

19. The process according to claim 18, wherein the binder is selected from the group consisting of poly(ethylene glycol) (PEG), poly(ethylene oxide) (PEO), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyacrylic acid (PAA), methylcellulose (MC), carboxymethylcellulose (CMC), CMC salts, hydroxypropylcellulose (HPC), hydroxyethylcellulose (HEC), and hydroxypropylmethylcellulose (HPMC), polytetrafluoroethylene (PTFE), and combinations thereof.

20. The process according to claim 18, wherein the precursor mixture comprises 0.025 to 1% by weight of a binder.

21. The process according to any one of claims 11 to 17, further comprising the step of stacking a plurality of the self-supporting precursor elements to form an element stack.

22. The process according to any one of claims 11 to 17, wherein the corrugated upper surface and the corrugated lower surface are continuous.

23. The process according to any one of claims 11 to 17, wherein the self-supporting precursor element has a density of 1.9 to 2.3 g / cm³.

24. The process according to any one of claims 11 to 17, wherein the self-supporting precursor element is placed on a substrate while being heated.

25. The process according to claim 24, wherein the self-supporting precursor element is transported through a high-temperature tunnel kiln when heated.

26. The process according to any one of claims 11 to 17, wherein the heating is carried out in an atmosphere selected from the group consisting of an oxidizing atmosphere, an inert atmosphere, and a reducing atmosphere.

27. ​​The process according to any one of claims 11 to 17, wherein the heating is carried out at a temperature of 650 to 850°C.

28. The process according to any one of claims 11 to 17, wherein the process includes a step of preheating the self-supporting precursor element.

29. The process according to any one of claims 11 to 17, wherein the process does not include an additional heating step of the cathode active material.

30. The process according to any one of claims 11 to 17, further comprising destroying the self-supporting calcination element to form calcination element powder.

31. The process according to claim 30, wherein the destruction includes a step selected from the group consisting of crushing, grinding, and combinations thereof.

32. The process according to any one of claims 11 to 17, further comprising processing the cathode active material.

33. The process according to claim 32, wherein the process comprises a step selected from the group consisting of sieving, washing, filtering, drying, coating, and combinations thereof.

34. A process for forming a cathode electrode, A step of incorporating the cathode active material according to any one of claims 11 to 17 into an electrode film, A process comprising the step of placing the electrode film on a current collector.

35. A process for forming an energy storage device, comprising the step of arranging a separator, an anode electrode and the cathode electrode according to claim 34 within a housing, The separator is placed between the anode electrode and the cathode electrode in the process.

36. The process according to claim 35, wherein the energy storage device is a battery.

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