Sintered cathode active material element and method

Abstract

Disclosed are free-standing fired elements (e.g., bricks and tiles) comprising cathode active material and methods for preparing the same. The process includes mixing reagents with metal precursors to form a precursor mixture, compressing the precursor mixture into free-standing precursor elements (e.g., bricks and tiles), and heating the free-standing precursor elements (e.g., bricks and tiles) to form free-standing fired elements (e.g., bricks and tiles) comprising cathode active material.

Description

[Technical Field] 【0001】 [Cross-reference of related applications] Any application in which a foreign or domestic priority claim is identified in the application data sheet or invoice filed with this application, such as U.S. Provisional Application No. 63 / 081,470 filed on 22 September 2020, is incorporated herein by reference under 37 CFR 1.57 and Rules 4.18 and 20.6. 【0002】 This disclosure generally relates to electrode active materials and processes for forming them. More specifically, this 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 typically involves baking the material in powder form at high temperatures through a large roller hearth kiln to obtain the desired material properties. This high-temperature process begins with a mixture of lithium compounds and a metal precursor to form a powder mixture. The powder is typically transported in a sheath (i.e., a large ceramic crucible), which is then fed into a long high-temperature kiln for a total residence time exceeding 12 hours. An exemplary schematic diagram of a sheath holding the cathode precursor powder shows a cathode powder height of approximately 80 mm and a load of approximately 0.9 kg / m³. 3 The bulk density is shown in Figure 1. The reacted material is then removed from the pod, ground to the target particle size, and optionally subjected to a surface treatment process before being supplied to the electrode manufacturing process. 【0004】 However, the firing process accounts for the highest portion of the manufacturing costs of all processes due to the highest capital costs, highest energy consumption, and long residence times of the roller hearth kilns (RHKs) that are typically used. Consequently, maximizing the processing capacity of these kilns is crucial to reducing the capital and operating costs of cathode production. 【0005】 Furthermore, the sheath itself introduces inefficiencies into the firing process. Standard dimensions for RHK sheaths are 100mm x 330mm x 330mm (H x W x L), with a usable height of ≤80mm and a total weight per sheath exceeding 5kg. The typical bulk density of the powder mixture is approximately 0.9g / cm³. 3 Typically, each stalk can only hold about 4.5 kg of mixed material, and high loads can affect gas diffusion and heat distribution, potentially leading to quality problems. While productivity can be improved by stacking the stalks (a typical industrial kiln configuration can accommodate rows of four stalks stacked in parallel in two tiers), such a productivity strategy is not scalable. 【0006】 Thus, sheaths have many inherent inefficiencies, including: 1) low heat and mass transfer coefficients as a result of powder stagnation within the crucible, further increasing the required residence time in the kiln; 2) cooling time at the kiln outlet is usually extended to prevent sheath cracking and extend sheath life; 3) high consumable costs as sheaths typically need to be replaced after 1-2 weeks of use; and 4) sheath handling and inspection systems are highly capital-intensive and can cause frequent downtime. 【0007】 Furthermore, firing may involve further processing to improve the crystallinity of the active material. While improved crystallinity of the active material typically correlates with improved energy storage device performance, further processing to improve crystallinity introduces further inefficiencies into the manufacturing process. [Overview of the Initiative] 【0008】 For the purpose of summarizing the advantages achieved beyond this disclosure and the prior art, specific purposes and advantages of this disclosure are described herein. Not all such purposes or advantages can be achieved in any particular embodiment. Therefore, for example, a person skilled in the art will recognize that the present invention may be embodied or implemented to achieve or optimize one advantage or set of advantages taught herein, without necessarily achieving other purposes or advantages that may be taught or suggested herein. 【0009】 All of these embodiments are intended to be within the scope of the invention disclosed herein. These and other embodiments will be readily apparent to those skilled in the art from the following detailed description of preferred embodiments with reference to the accompanying drawings, and the invention is not limited to any particular preferred embodiment disclosed. 【0010】 In one embodiment, a self-supporting firing element is described. The self-supporting firing element contains at least about 95% by weight of cathode active material. 【0011】 In some embodiments, the cathode active material comprises crystalline cathode active material particles. In some embodiments, 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. In some embodiments, the freestanding sintered element contains up to about 1 wt% residual lithium. In some embodiments, the freestanding sintered element contains about 0.1 to 1 wt% binder. In some embodiments, the freestanding sintered element is substantially binder-free. 【0012】 In some embodiments, the freestanding fired element includes multiple through holes. In some embodiments, the freestanding fired element includes 2 to 50 through holes. In some embodiments, each of the multiple through holes has a diameter of approximately 10 to 30 mm. In some embodiments, the freestanding fired element includes multiple through holes in approximately 0.1 to 30% of the total element volume. In some embodiments, the freestanding fired element includes a surface pattern configured to form at least one channel between adjacent elements. In some embodiments, the freestanding fired element is in the shape of a brick or tile. In some embodiments, the freestanding fired element has a density of approximately 1.9 to 2.3 g / cm³ 3 This includes the density of the freestanding fired element, which in some embodiments is approximately 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 process includes mixing a reagent with a metal precursor to form a precursor mixture, compressing the precursor mixture to form a self-supporting precursor element, and heating the self-supporting precursor element to form a self-supporting calcined element containing a cathode active material. 【0014】 In some embodiments, the reagent is a lithium reagent. In some embodiments, the lithium reagent is selected from the group consisting of lithium hydroxide, lithium hydroxide monohydrate, lithium carbonate, and combinations thereof. In some embodiments, the metal precursor is selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, and combinations thereof. In some embodiments, the metal precursor includes a metal selected from the group consisting of Ni, Mn, Co, Al, Mg, Fe, Ti, and 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 contains about 0.1 to 20% by weight of the solvent. In some embodiments, the precursor mixture further comprises a binder. In some embodiments, 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. In some embodiments, the precursor mixture contains about 0.1 to 1% by weight of the binder. In some embodiments, the precursor mixture contains about 0.025 to 1% by weight of the binder. In some embodiments, the freestanding precursor element contains a plurality of through-holes. In some embodiments, the process further comprises stacking a plurality of freestanding precursor elements to form an element stack. In some embodiments, the element stack includes at least one channel between adjacent freestanding precursor elements. In some embodiments, the freestanding precursor elements have a density of approximately 1.9–2.3 g / cm³. 3 It includes the density of. 【0016】 In some embodiments, the freestanding precursor element is supported by a substrate while being heated. In some embodiments, the freestanding precursor element is transported through a high-temperature tunnel kiln once heated. In some embodiments, heating is carried out in an atmosphere selected from the group consisting of an oxidizing atmosphere, an inert atmosphere, and a reducing atmosphere. In some embodiments, heating is carried out in an oxygen-containing atmosphere. In some embodiments, heating is carried out at a temperature of about 650–850°C. In some embodiments, the process includes preheating the freestanding precursor element. In some embodiments, the process does not include an additional heating step of the cathode active material. 【0017】 In some embodiments, the process further includes destroying self-supporting calcination elements to form calcination element powder. In some embodiments, the destruction includes steps selected from the group consisting of crushing, grinding, and combinations thereof. In some embodiments, the process further includes processing the cathode active material. In some embodiments, the processing includes steps selected from the group consisting of sieving, washing, filtering, drying, coating, and combinations thereof. 【0018】 In another embodiment, a process for forming a cathode electrode is described. This process includes incorporating the cathode active material described herein into an electrode film and arranging the electrode film on a current collector. 【0019】 In another embodiment, a process for forming an energy storage device is described. This process includes arranging a separator, an anode electrode, and a cathode electrode as described herein within a housing, the separator being positioned 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 and heated to produce freestanding fired elements (e.g., bricks and tiles) containing the cathode active material, which exhibits improved crystallinity. For example, in some embodiments, a mixture of lithium and metal powder is formed into freestanding or capable freestanding elements (e.g., bricks and tiles) and then transported through a high-temperature furnace. In some embodiments, the elements (e.g., precursor, pre-baked elements and / or fired elements) may be any freestanding geometric shape or form, such as bricks and / or tiles. 【0037】 The use of self-supporting elements (e.g., bricks and tiles) allows for the removal of sheaths from the manufacturing process, resulting in numerous improvements in manufacturing, including: 1) increased volumetric efficiency of the sintering process; 2) increased processing capacity of typical industrial kilns; 3) reduced heat mass required for heating and cooling in each cycle; 4) increased thermal conductivity of the powder mixture fed into the furnace; 5) increased thermal uniformity; 6) reduced required process residence time; and 7) reduced consumable costs by simplifying the geometric shape of the support (e.g., sheath vs. plate). precursor mixture 【0038】 Prior to the formation of the element, in one embodiment, a precursor mixture including a reagent and a metal precursor 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 selected from metal oxides (M x O n ), metal hydroxides (M x (OH) n ), metal carbonates (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 includes a metal ("M") selected from Ni, Mn, Co, Al, Mg, Fe, Ti, and combinations thereof. 【0039】 In some embodiments, the precursor mixture further includes a solvent. In some embodiments, the solvent can help maintain the shape of the element formed from the precursor mixture through the firing process. In some embodiments, the solvent is water. In some embodiments, the precursor mixture includes 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%, 0.5 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, the precursor mixture does not include or substantially does not include a solvent or added solvent. In some embodiments, the precursor mixture does not include or substantially does not include water or added water. For example, in some embodiments, a precursor mixture that does not substantially include water or added water can include water absorbed from atmospheric moisture. 【0040】 In some embodiments, the precursor mixture further comprises a binder. In some embodiments, the binder may help maintain the shape of the elements formed from the precursor mixture throughout the calcination process. In some embodiments, the binder comprises a polymer material. In some embodiments, the binder comprises a water-soluble polymer material. In some embodiments, the binder comprises a polymer material selected from poly(ethylene glycol) (PEG), poly(ethylene oxide) (PEO), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyacrylic acid (PAA), methylcellulose (MC), carboxymethylcellulose (CMC) and their salts (e.g., sodium CMC), hydroxypropylcellulose (HPC), hydroxyethylcellulose (HEC), and hydroxypropylmethylcellulose (HPMC), polytetrafluoroethylene (PTFE), and combinations thereof. In the mixing embodiment, the polymer material is 20000, 25000, 28000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 110000, 1200000, 1300000, 1400000, 1600000 or 2000000, or about 20 It has a weight-average molecular weight of 000, 25000, 28000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 110000, 1200000, 1300000, 1400000, 1600000 or 2000000, or any range of values ​​in between.In some embodiments, the precursor mixture is 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, 0.08% by weight, 0.09% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 1% by weight, 1.2% by weight, 1.5% by weight or 2% by weight, or about 0 Includes binders of values ​​ranging from 0.01 weight, 0.02 weight%, 0.025 weight%, 0.3 weight%, 0.04 weight%, 0.05 weight%, 0.06 weight%, 0.07 weight%, 0.08 weight%, 0.09 weight%, 0.1 weight%, 0.2 weight%, 0.3 weight%, 0.4 weight%, 0.5 weight%, 0.6 weight%, 0.7 weight%, 0.8 weight%, 1 weight%, 1.2 weight%, 1.5 weight%, or 2 weight%, or any range of values ​​in between. 【0041】 In some embodiments, the precursor mixture further comprises additives. In some embodiments, the additives include elements selected from Fe, Ti, and combinations thereof. Precursor and calcination elements 【0042】 From a precursor mixture, a precursor or raw element is formed, and the element is self-supporting or capable of self-supporting. In some embodiments, a self-supporting precursor brick is heated in a pre-baking or preheating step to form a self-supporting pre-baked element. Furthermore, the self-supporting precursor or pre-baked element can then be heated to react a reagent with a metal precursor to form a self-supporting calcined element, the calcined element containing a cathode active material. The precursor element contains the same or substantially the same composition as the precursor mixture from which it is formed. A self-supporting or capable of self-supporting element is understood as an element that maintains its shape and structure by its own weight. 【0043】 Figures 2A and 2B are photographic images of bricks without water and binder according to several embodiments, and Figures 2C and 2D are images of bricks with water and binder according to several embodiments. In Figure 2A, the dry brick formed from the mixture without water and binder is formed into a freestanding precursor brick. In this embodiment, the precursor brick is 1.7 g / cm³ 3 It was found to have a density of approximately 1.8 g / cm³. However, the dried brick in Figure 2A did not maintain the formed brick structure and collapsed over time as shown in Figure 2B. In contrast, Figure 2C shows a brick with a density of approximately 1.8 g / cm³. 3 This shows a brick containing water and binder formed at a density of . This brick was found to substantially maintain its structure over time, as shown in Figure 2D. The bricks shown in Figures 2C and 2D can be considered to be self-supporting as described herein. 【0044】 In some embodiments, the freestanding precursor element includes a plurality of through holes. Figure 3A is a schematic diagram of a freestanding precursor brick including a plurality of through holes according to some embodiments. Figure 3B is a schematic diagram showing such freestanding precursor bricks including a plurality of through holes stacked in sequence. In some embodiments, the freestanding precursor element includes a surface pattern such that when the elements are stacked, at least one channel is formed between adjacent elements. 【0045】 Figure 4A is a schematic diagram of a freestanding precursor tile having a wavefront pattern according to several embodiments. Figure 4B is a schematic diagram of such a freestanding precursor tile having a wavefront pattern such that when the tiles are stacked, multiple channels are formed between adjacent stacked tiles. 【0046】 Precursor elements (or in any form, e.g., during the precursor, pre-bake, firing, or any other step of the disclosed process) may include at least one through-hole and / or surface pattern that allows for the formation of at least one channel when stacked. Such through-holes and / or channels between stacked bricks or tiles can facilitate the diffusion of air (e.g., an oxidizing atmosphere (e.g., containing oxygen), an inert atmosphere, or a reducing atmosphere) into the elements and the release of moisture from the elements. For example, oxygen diffusion into the precursor elements can facilitate oxygen consumption as part of the reaction that forms the cathode active material, and the through-holes and / or channels may allow O2 to access the reagent within and / or at the center of the elements, while allowing the rest of the elements to maintain a high packing density. Furthermore, since H2O is produced as part of the reaction that forms the cathode active material, the through-holes and / or channels may allow moisture to leak out from the interior and / or center of the elements, thereby resulting in the final material properties of the elements after heating. For example, in some embodiments, the through-holes and / or channels can prevent cracking of the elements after baking. 【0047】 In some embodiments, the freestanding precursor element includes 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, or through-holes with values ​​in any range between them. In some embodiments, each of the multiple through-holes has a diameter of 1 mm, 5 mm, 10 mm, 15 mm, 20 mm, 25 mm, 30 mm, 40 mm, 50 mm, 75 mm, or 100 mm, or approximately 1 mm, 5 mm, 10 mm, 15 mm, 20 mm, 25 mm, 30 mm, 40 mm, 50 mm, 75 mm, or 100 mm, or any range between them. In some embodiments, each of the multiple through holes is spaced from the other through holes by 10 mm, 11 mm, 12 mm, 13 mm, 14 mm, 15 mm, 17 mm, 20 mm, 25 mm, 30 mm, 35 mm, 40 mm, 45 mm, 50 mm, 60 mm, 65 mm, 70 mm, 75 mm, 80 mm, 85 mm, 90 mm, 95 mm, 100 mm, 120 mm, 150 mm or 200 mm, or approximately 10 mm, 11 mm, 12 mm, 13 mm, 14 mm, 15 mm, 17 mm, 20 mm, 25 mm, 30 mm, 35 mm, 40 mm, 45 mm, 50 mm, 60 mm, 65 mm, 70 mm, 75 mm, 80 mm, 85 mm, 90 mm, 95 mm, 100 mm, 120 mm, 150 mm or 200 mm, or any range of values ​​in between. In some embodiments, the through-holes are uniformly distributed through the element on at least one surface of the element, or substantially uniformly distributed.In some embodiments, the elements comprise 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 8%, 10%, 15%, 20%, 25%, 30%, or 40% of the total element volume, 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. The elements include through-holes with values ​​of 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 any range of values ​​in between. In some embodiments, the freestanding elements do not include through-holes. 【0048】 In some embodiments, an adjacent pair of freestanding precursor elements includes 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 about 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 channels with values ​​in any range between them. In some embodiments, each of the multiple channels has characteristic dimensions (e.g., length, width, diameter) as viewed from outside the element stack of 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 11 mm, 12 mm, 13 mm, 14 mm, 15 mm, 17 mm, 20 mm, 25 mm, 30 mm, 35 mm, 40 mm, 45 mm, 50 mm, 60 mm, 70 mm, 75 mm, or 100 mm, or approximately 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 11 mm, 12 mm, 13 mm, 14 mm, 15 mm, 17 mm, 20 mm, 25 mm, 30 mm, 35 mm, 40 mm, 45 mm, 50 mm, 60 mm, 70 mm, 75 mm, or 100 mm, or any range in between. In some embodiments, each of the multiple channels is spaced apart from another channel by a value of 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 or 200mm, or any range in between. In some embodiments, at least one of the multiple channels extends the length of an adjacent pair of freestanding elements. In some embodiments, each of the multiple channels extends across the length of an adjacent pair of freestanding elements.In some embodiments, the freestanding precursor element does not include through holes. 【0049】 In some embodiments, the freestanding precursor element has a thickness of 0.5 mm, 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 8 mm, 10 mm, 20 mm, 40 mm, 60 mm or 100 mm, approximately 0.5 mm, 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 8 mm, 10 mm, 20 mm, 40 mm, 60 mm or 100 mm, up to 0.5 mm, 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 8 mm, 10 mm, 20 mm, 40 mm, 60 mm or 100 mm, or up to approximately 0.5 mm, 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 8 mm, 10 mm, 20 mm, 40 mm, 60 mm or 100 mm, or any range of values ​​in between. 【0050】 In some embodiments, the freestanding precursor element is 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 / 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 2.3 g / cm³ 3 2.4 g / cm³ 3 2.6 g / cm³ 3 2.8 g / cm³ 3 , 3g / cm³ 3 3.5 g / cm³ 3 , 4g / cm³ 3 4.5 g / cm³ 3 Or 5g / cm³ 3 , or approximately 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 / cm³ 3 1.7 g / cm³ 31.8 g / cm³ 3 1.9 g / cm³ 3 , 2g / cm³ 3 , 2.2 g / cm³ 3 2.3 g / cm³ 3 2.4 g / cm³ 3 2.6 g / cm³ 3 2.8 g / cm³ 3 , 3g / cm³ 3 3.5 g / cm³ 3 , 4g / cm³ 3 4.5 g / cm³ 3 Or 5g / cm³ 3 This includes densities of any range of values ​​between these. In some embodiments, the element density is the density of the element's material excluding through holes. 【0051】 In some embodiments, the self-supporting firing element contains 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, 99.2% by weight, 99.5% by weight, 99.8% by weight, 99.9% by weight or 100% by weight of cathode active material, approximately 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, 99.2% by weight, 99.5% by weight, 99.8% by weight, 99.9% by weight or 100% by weight of cathode active material, at least 90 by weight The cathode active material comprises %, 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, 99.2% by weight, 99.5% by weight, 99.8% by weight, 99.9% by weight or 100% by weight, or at least about 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, 99.2% by weight, 99.5% by weight, 99.8% by weight, 99.9% by weight or 100% by weight, or cathode active material in any range of values ​​between those. In some embodiments, the cathode active material comprises crystalline cathode active material particles. In some embodiments, the freestanding firing element contains 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 of crystalline cathode active material particles, approximately 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 of crystalline cathode active material particles, at least 50% by weight, 6 The material comprises crystalline cathode active material particles in amounts of 0 wt%, 70 wt%, 80 wt%, 90 wt%, 95 wt%, 98 wt%, 99 wt%, or 100 wt%, or at least approximately 50 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, 95 wt%, 98 wt%, 99 wt%, or 100 wt%, or crystalline cathode active material particles in any range of values ​​between those amounts.In some embodiments, the cathode active material is selected from 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 a combination thereof. 【0052】 In some embodiments, the freestanding firing element contains 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, 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, 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 of lithium reagent, or lithium reagent in any range of values ​​between these. In some embodiments, the freestanding firing element contains 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, 0.5 wt%, or 0.1 wt% of a metal precursor, about 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, 0.5 wt%, or 0.1 wt% of a metal precursor, up to 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, 0.5 wt%, or 0.1 wt% of a metal precursor, or up to about 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, 0.5 wt%, or 0.1 wt% of a metal precursor, or a metal precursor in any range of values ​​between them. In some embodiments, the freestanding firing element contains no or substantially no water. In some embodiments, the freestanding firing element contains 1% by weight, 0.5% by weight, 0.1% by weight, or 0.01% by weight of water, about 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 about 1% by weight, 0.5% by weight, 0.1% by weight, or 0.01% by weight of water, or any range of values ​​in between.In some embodiments, the freestanding firing element contains binders of 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, or 2 wt%, approximately 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, or 2 wt%, up to 0.0 The binder may be 1% 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, 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, or 2% by weight, or any range of values ​​between them. In some embodiments, the freestanding fired element may not contain or may not contain any binder. In some embodiments, the freestanding fired element may contain a decomposed binder residue. In some embodiments, the freestanding firing element does not contain or substantially contains decomposed binder residue. In some embodiments, the freestanding firing element contains residual lithium in amounts of 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt%, 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, 0.5 wt%, or 0.1 wt%, approximately 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt%, 5 wt%, 4 wt%, 3 wt%, 2 wt%, or 1 wt%, up to 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt%, 5 wt%, 4 wt%, 3 wt%, 2 wt%, or 1 wt%, or up to approximately 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt%, 5 wt%, 4 wt%, 3 wt%, 2 wt%, or 1 wt%, or any range of values ​​between them. 【0053】 In some embodiments, the freestanding fired element includes a plurality of through holes. In some embodiments, the freestanding fired element includes a surface pattern such that when the elements are stacked, at least one channel is formed between adjacent elements. In some embodiments, the plurality of through holes and / or channels of the freestanding fired element are retained or substantially retained from the freestanding precursor element. In some embodiments, the freestanding fired element includes 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, or through holes of any range of values ​​between them. In some embodiments, each of the multiple through holes has a diameter of 1 mm, 5 mm, 10 mm, 15 mm, 20 mm, 25 mm, 30 mm, 40 mm, 50 mm, 75 mm, or 100 mm, or approximately 1 mm, 5 mm, 10 mm, 15 mm, 20 mm, 25 mm, 30 mm, 40 mm, 50 mm, 75 mm, or 100 mm, or any range in between. In some embodiments, each of the multiple through holes is spaced from the other through holes by 10 mm, 11 mm, 12 mm, 13 mm, 14 mm, 15 mm, 17 mm, 20 mm, 25 mm, 30 mm, 35 mm, 40 mm, 45 mm, 50 mm, 60 mm, 65 mm, 70 mm, 75 mm, 80 mm, 85 mm, 90 mm, 95 mm, 100 mm, 120 mm, 150 mm or 200 mm, or approximately 10 mm, 11 mm, 12 mm, 13 mm, 14 mm, 15 mm, 17 mm, 20 mm, 25 mm, 30 mm, 35 mm, 40 mm, 45 mm, 50 mm, 60 mm, 65 mm, 70 mm, 75 mm, 80 mm, 85 mm, 90 mm, 95 mm, 100 mm, 120 mm, 150 mm or 200 mm, or any range of values ​​in between. In some embodiments, the through-holes are uniformly distributed through the element on at least one surface of the element, or substantially uniformly distributed.In some embodiments, the element has through holes representing 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 8%, 10%, 15%, 20%, 25%, or 30% of the total element volume, approximately 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 8%, 10%, 15%, 20%, 25%, or 30% of the total element volume, and at least 0. The through-holes include 1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 8%, 10%, 15%, 20%, 25%, or 30%, or at least approximately 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 8%, 10%, 15%, 20%, 25%, or 30%, or through-holes in any range of values ​​between them. In some embodiments, the freestanding fired element does not contain through-holes. 【0054】 In some embodiments, an adjacent pair of freestanding firing elements includes 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, or 50 channels, or channels with values ​​in any range between them. In some embodiments, each of the multiple channels has characteristic dimensions (e.g., length, width, diameter) as viewed from outside the element stack of 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 11 mm, 12 mm, 13 mm, 14 mm, 15 mm, 17 mm, 20 mm, 25 mm, 30 mm, 35 mm, 40 mm, 45 mm, 50 mm, 60 mm, 70 mm, 75 mm, or 100 mm, or approximately 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 11 mm, 12 mm, 13 mm, 14 mm, 15 mm, 17 mm, 20 mm, 25 mm, 30 mm, 35 mm, 40 mm, 45 mm, 50 mm, 60 mm, 70 mm, 75 mm, or 100 mm, or any range in between. In some embodiments, each of the multiple channels is spaced apart from another channel by a value of 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 or 200mm, or any range in between. In some embodiments, at least one of the multiple channels extends the length of an adjacent pair of freestanding elements. In some embodiments, each of the multiple channels extends across the length of an adjacent pair of freestanding elements.In some embodiments, the freestanding precursor element does not include through holes. 【0055】 In some embodiments, the freestanding firing element has a thickness of 0.5 mm, 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 8 mm, 10 mm, 20 mm, 40 mm, 60 mm or 100 mm, approximately 0.5 mm, 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 8 mm, 10 mm, 20 mm, 40 mm, 60 mm or 100 mm, up to 0.5 mm, 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 8 mm, 10 mm, 20 mm, 40 mm, 60 mm or 100 mm, or up to approximately 0.5 mm, 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 8 mm, 10 mm, 20 mm, 40 mm, 60 mm or 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 / cm³ 3 1.7 g / cm³ 3 1.75 g / cm³ 3 1.8 g / cm³ 3 1.9 g / cm³ 3 , 2g / cm³ 3 , 2.2 g / cm³ 3 2.3 g / cm³ 3 2.4 g / cm³ 3 2.6 g / cm³ 3 2.8 g / cm³ 3 , 3g / cm³ 3 3.5 g / cm³ 3 , 4g / cm³ 3 4.5 g / cm³ 3 5g / cm³ 3 5.5 g / cm³ 3 Alternatively, 6 g / cm³ 3 , or approximately 0.8 g / cm³ 3 , 0.9 g / cm³ 3, 1 g / cm 3 , 1.2 g / cm 3 , 1.3 g / cm 3 , 1.4 g / cm 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 3 , 3 g / cm 3 , 3.5 g / cm 3 , 4 g / cm 3 , 4.5 g / cm3, 5 g / cm 3 , 5.5 g / cm 3 or 6 g / cm 3 , or includes a density value within any range therebetween. In some embodiments, the self-standing fired element is crack-free or substantially crack-free. 【0057】 In some embodiments, the self-standing precursor element can be heated before forming the self-standing pre-baked element and then heated to form the self-standing fired element. The preheating of the element, if the precursor is not pre-oxidized, is dehydration of free water, decomposition of LiOH·H2O to LiOH, and / or decomposition of metal hydroxide precursors (e.g., Ni 0.83 Mn 0.06 Co 0.11 (OH)2) to metal oxide precursors (e.g., Ni 0.83 Mn 0.06 Co<000This can help decompose into O). In some embodiments, the freestanding pre-baked elements may include through-holes and surface patterns that allow for at least one channel when stacked, as described with respect to the precursor and / or calcined elements. In some embodiments, the freestanding pre-baked elements may include other properties (e.g., dimensions, density and / or chemical composition) that are similar to or the same as those described with respect to the precursor and / or calcined elements. Element and cathode active material formation step 【0058】 Figure 4 is a flowchart showing an example of cathode material formation through a formation process according to several embodiments. Reagents 402 and precursors 404 are provided and mixed 406 to form a mixture. Examples of reagents 402 include LiCO3, LiOH, and LiOH·H2O, and examples of precursors include metal oxides (MO n ), metal hydroxide (M(OH) n ), and metal carbonates (M(CO3) n ) are examples. After the mixture is formed in the mixing step 406, this mixture is used to form precursor elements that are loaded onto a plate or substrate in the element fabrication and stacking step 408. The elements are then heated in the calcination step 410 to form calcined elements. The calcined elements are removed from the substrate and broken down to form calcined element powder in the plate flip and size reduction step 412, the substrate is inspected and returned to the element fabrication and stacking step 408 in the plate return and inspection step 414. The calcined element powder is surface treated in the surface treatment step 416 to form the cathode active material LiMeO2418. 【0059】 In some embodiments, the process includes mixing a reagent with a metal precursor to form a precursor mixture. In some embodiments, the process includes compressing the precursor mixture to form a precursor element. In some embodiments, the process includes heating the precursor element to form a calcined element containing a cathode active material. In some embodiments, the precursor element and / or calcined element are freestanding elements. 【0060】 In some embodiments, the process includes modifying a precursor element to include through-holes. In some embodiments, the precursor element is supported by a substrate while being heated. 【0061】 In some embodiments, precursor elements are transported through tunnel kilns (e.g., low-temperature and / or high-temperature tunnel kilns). In some embodiments, precursor or pre-bake elements are heated within the high-temperature tunnel kiln. In some embodiments, the low-temperature and high-temperature kilns are the same kiln set to different temperatures. In some embodiments, the low-temperature and high-temperature kilns are different kilns. In some embodiments, heating is carried out in an oxidizing atmosphere (e.g., an oxygen-containing atmosphere, e.g., air or an oxygen-rich atmosphere (i.e., more than 21 vol%, more than 23.5 vol%, or more than 25 vol% oxygen)), an inert atmosphere (e.g., an atmosphere containing helium, neon, argon, krypton, xenon, radon, and / or nitrogen) or a reducing atmosphere (e.g., an atmosphere containing hydrogen, carbon monoxide, and / or hydrogen sulfide). For example, in some embodiments, the formation of lithium iron phosphate (LFP) is carried out by heating (e.g., calcination) in an inert or reducing atmosphere. In some embodiments, gas passes through through holes and / or channels during the pre-bake and / or calcination heating of the elements. In some embodiments, the gas includes an oxidizing gas (e.g., oxygen, such as air or an oxygen-rich atmosphere), an inert gas, or a reducing gas. In some embodiments, the heating is 700°C, 725°C, 750°C, 760°C, 780°C, 800°C, 820°C, 840°C, 850°C, 860°C, 880°C, 900°C, 950°C, or 1000°C, about 700°C, 725°C, 750°C, 760°C, 780°C, 800°C, 820°C, 840°C, 850°C, 860°C, 880°C, 900°C, 950°C, or 1000°C, at least 700°C, 7 The process is carried out at temperatures of 25°C, 750°C, 760°C, 780°C, 800°C, 820°C, 840°C, 850°C, 860°C, 880°C, 900°C, 950°C, or 1000°C, or at least approximately 700°C, 725°C, 750°C, 760°C, 780°C, 800°C, 820°C, 840°C, 850°C, 860°C, 880°C, 900°C, 950°C, or 1000°C, or any range of values ​​in between. In some embodiments, the process includes preheating a self-supporting precursor element. 【0062】 In some embodiments, precursor elements are heated in a low-temperature tunnel kiln during a pre-baking or preheating step to form pre-baked elements (e.g., bricks and tiles). In some embodiments, the pre-baking step is performed before the firing heating of the elements. In some embodiments, the firing heating of the elements further includes the pre-baking step. In some embodiments, preheating is performed at a temperature lower than the firing heating temperature. In some embodiments, heating is performed at 80°C, 100°C, 120°C, 140°C, 160°C, 180°C, 200°C, 220°C, 230°C, 240°C, 250°C, 260°C, 280°C, 300°C, 320°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 650°C, 700°C, or 75°C. 0°C, approximately 80°C, 100°C, 120°C, 140°C, 160°C, 180°C, 200°C, 220°C, 230°C, 240°C, 250°C, 260°C, 280°C, 300°C, 320°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 650°C, 700°C or 750°C, at least 80°C, 1 It is performed at temperatures of 00°C, 120°C, 140°C, 160°C, 180°C, 200°C, 220°C, 230°C, 240°C, 250°C, 260°C, 280°C, 300°C, 320°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 650°C, 700°C or 750°C, at least approximately 80°C, 100°C, 120°C, 140°C, 160°C, 180°C, 200°C, 220°C, 230°C, 240°C, 250°C, 260°C, 280°C, 300°C, 320°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 650°C, 700°C or 750°C, or any range of values ​​in between. In some embodiments, the process does not involve an additional heating step of the cathode active material. In some embodiments, a gas passes through through holes and / or channels during the pre-bake and / or firing heating of the element. In some embodiments, the gas includes oxygen (e.g., air). In some embodiments, the freestanding pre-bake and / or firing element is crack-free or substantially crack-free.In some embodiments, heating (e.g., pre-baking and / or calcination) decomposes (e.g., burns and / or carbonizes) the binder in the precursor element and / or pre-baked element. In some embodiments, the decomposed binder residue is vaporized from the pre-baked element and / or calcined element. In some embodiments, at least a portion (e.g., a measurable amount) of the decomposed binder residue remains in the pre-baked element and / or calcined element. In some embodiments, the pre-baked element and / or calcined element does not contain or substantially contains the decomposed binder residue. In some embodiments, heating reduces the density of the element. 【0063】 In some embodiments, the process includes destroying a self-supporting calcined element to form a calcined element powder. In some embodiments, the destruction includes steps selected from crushing, grinding, and combinations thereof. In some embodiments, the process includes processing the cathode active material. In some embodiments, the processing includes steps selected from sieving, washing, filtering, drying, coating, and 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 methods selected from spray coating, mechanical fusion, and combinations thereof. 【0064】 Figures 5A to 5D show images of various bricks with through holes at different stages of the forming process according to several embodiments. Figure 5A shows a press-formed precursor brick, and Figure 5B shows a pre-baked brick. Figure 5C shows a fired brick that retained its shape throughout the firing process, and Figure 5D shows a fired brick that did not retain its shape throughout the firing process and shows cracks and fissures. Figures 6A and 6B show images of stacked fired tiles that retained their shape throughout the firing process and stacked tiles that did not retain their shape throughout the firing process, respectively. Energy storage devices 【0065】 Once the cathode active material is isolated, it can be used to prepare electrodes for energy storage devices. In some embodiments, the electrode film comprises 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 comprises a binder. In some embodiments, the electrode comprises a current collector and the electrode film described herein. In some embodiments, the electrode film is placed on the current collector to form a cathode electrode. 【0066】 In some embodiments, the energy storage device utilizes the cathode active material described herein. In some embodiments, the energy storage device includes a separator, an anode electrode, the cathode electrode described herein, and a housing, wherein the separator, anode electrode, and cathode electrode are arranged within the housing, and the separator is positioned between the anode electrode and the cathode electrode. In some embodiments, the energy storage device is formed by arranging the separator, anode electrode, and the cathode electrode described herein within the housing, and the separator is positioned 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. [Examples] 【0067】 Exemplary embodiments of the present disclosure, including processes, materials, and / or resulting products, are described in the following examples. Example 1 【0068】 Micron-sized powdered lithium carbonate and electrolytic manganese dioxide (EMD) were mixed at a molar ratio of Li / Mn = 1.05, and then 1.8 g / cm³ was added to a 100 mm (H) × 150 mm (W) × 300 mm (L) area. 3The material was compressed into self-supporting, unprocessed bricks with a density of . The unprocessed bricks were then stacked on ceramic plates and placed in a kiln, where they were fired in air at 850°C for 18 hours. After cooling, the self-supporting fired bricks were crushed, ground into a powder, and then sieved through a 400-mesh sieve to obtain the final product, spinel LiMn2O4 (LMO), as a cathode material for lithium-ion batteries. 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 the O (dehydration precursor), it was mixed with lithium carbonate at a molar ratio of Li / Mn = 1.08. To improve the integrity of the brick, 15% by weight of water was added to the mixture at the end of the mixing step. The mixture was then packed at a density of 2.5 g / cm³ in a container measuring 100 mm (H) × 150 mm (W) × 300 mm (L). 3 The material was compressed into self-supporting, unprocessed bricks having a density of . The unprocessed bricks were then stacked on ceramic plates and placed in a kiln, where they were fired at 880°C for 12 hours while air was flowing through them. After cooling, the self-supporting fired bricks were crushed, ground into powder, and then sieved through a 400-mesh sieve to obtain the final product of layered NMC532 cathode material for lithium-ion batteries. 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. The mixture was then measured at 2.2 g / cm³ in a container measuring 300 mm (L) × 50 mm (W) × 150 mm (H). 3The material was compressed into self-supporting, unprocessed bricks having a density of . The unprocessed bricks were then stacked on ceramic plates and placed in a kiln, where they were fired at 850°C for 12 hours while dry air was flowed through them. After cooling, the self-supporting fired bricks were crushed, ground into a powder, and then sieved through a 400-mesh sieve to obtain the final product of layered NMC622 cathode material for lithium-ion batteries. Example 4 【0071】 Lithium hydroxide monohydrate and Ni 0.6 Mn 0.6 Co 0.2 (OH)2 is mixed with Li / Mn in a molar ratio of 1.06, and a 4 wt% aqueous solution is added to the mixture at the end of the mixing step, where the aqueous solution contains 5 wt% polyvinyl alcohol (PAV). The mixture is then measured at 2.0 g / cm³ in a container measuring 100 mm (H) × 150 mm (W) × 300 mm (L). 3 The material was compressed into self-supporting, unprocessed bricks with a density of 12 cylindrical through-holes (diameter = 20 mm) uniformly distributed along the length of the bricks. The unprocessed bricks were then stacked on a ceramic plate and placed in a kiln, where they were fired at 850°C for 12 hours while dry air was flowed through them. After cooling, the self-supporting fired bricks were crushed, ground into a powder, and then sieved through a 400-mesh sieve to obtain the final product of 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 is mixed with Li / Mn in a molar ratio of 1.02, and a 4 wt% aqueous solution is added to the mixture by the end of the mixing step, where the aqueous solution contains 2 wt% sodium carboxymethylcellulose (CMC). The mixture is then measured at 2.5 g / cm³ in a container measuring 100 mm (H) × 150 mm (W) × 300 mm (L). 3The material was compressed into freestanding, unprocessed bricks, and 12 square through-holes (side length = 20 mm) were uniformly distributed along the length of the bricks. The unprocessed bricks were then stacked on ceramic plates and placed in a kiln, where they were fired at 780°C for 12 hours while oxygen was flowing through them. After cooling, the freestanding fired bricks were crushed, ground into powder, then sieved through a 400-mesh sieve, followed by a surface treatment process including washing, filtration, and drying, and then passed through a mechanical fusion machine to be 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 was mixed with Mn at a molar ratio of Li / Mn = 1.02. Then, the powder was measured at a density of 1.8 g / cm³ in a container measuring 100 mm (H) × 150 mm (W) × 300 mm (L). 3 The material was compressed into freestanding, unprocessed bricks. The unprocessed bricks were then stacked on ceramic plates and placed in a kiln, where they were fired at 760°C for 12 hours with oxygen flowing through them. After cooling, the bricks were crushed, ground into powder, then sieved through a 400-mesh sieve, followed by a surface treatment process including washing, filtration, and drying, and then passed through a mechanical fusion machine to be coated with 0.3 wt% nano-sized Al2O3. Example 7 【0074】 LiOH·H2O, Ni 0.83 Mn 0.06 Co 0.11 A mixture of (OH)2, sodium carboxymethylcellulose (CMC) as a binder additive, and water was prepared and compressed into tiles. LiOH·H2O and Ni 0.83 Mn 0.06 Co 0.11 The molar ratio with (OH)2 was 1.055. The weight of the CMC additive was LiOH·H2O and Ni 0.83 Mn 0.06 Co 0.11 It is 0.25% of the total weight with (OH)2, and the weight of water is LiOH·H2O and Ni 0.83 Mn 0.06 Co 0.11It 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 A mixture of (OH)2 and CMC was dry-mixed, and then water was added during mixing. The wet mixture was filled into a mold and then pressed into tiles with the designed geometric shape. The thickness of the pressed tiles was 10-50 mm, and the bulk density was 2.20 g / cm³. 3 That was the case. 【0076】 These precursor tiles were self-supporting, and six of them were stacked and placed in a kiln while hot air at 250°C was flowed over them for pre-baking. After pre-baking, the self-supporting pre-baked tiles were placed in a roller hearth kiln (RHK) in a controlled atmosphere for firing. Subsequently, the self-supporting fired tiles were crushed, pulverized, filtered, washed, and dried to isolate the active material. 【0077】 Such mixtures have been demonstrated to achieve self-supporting precursor tiles that remain upright when stacked, pre-baked, and fired. Comparative Example 【0078】 LiOH·H2O, Ni 0.83 Mn 0.06 Co 0.11 A mixture of (OH)2, sodium carboxymethylcellulose (CMC) as a binder additive, and water was prepared and compressed into tiles. LiOH·H2O and Ni 0.83 Mn 0.06 Co 0.11 The molar ratio with (OH)2 was 1.030. The weight of the CMC additive was LiOH·H2O and Ni 0.83 Mn 0.06 Co 0.11 It is 0.05% of the total weight with (OH)2, and the weight of water is LiOH·H2O and Ni 0.83 Mn 0.06 Co 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 A mixture of (OH)2 and CMC was dry-mixed, and then water was added during mixing. The wet mixture was filled into a mold and then pressed into tiles with the designed geometric shape. The thickness of the pressed tiles was 10-50 mm, and the bulk density was 1.90 g / cm³. 3 That is the case. 【0080】 Such mixtures have been shown to produce precursor tiles that do not remain self-supporting when stacked, pre-baked, and fired. 【0081】 While specific embodiments have been described, these embodiments are presented as examples only and are not intended to limit the scope of this disclosure. In fact, the novel methods and systems described herein may be embodied in a variety of other forms. Furthermore, various omissions, substitutions, and modifications may be made to the systems and methods described herein without departing from the spirit of this disclosure. The appended claims and their equivalents are intended to encompass forms or modifications that fall within the scope and spirit of this disclosure. 【0082】 Any feature, material, property, or group described in relation to a particular aspect, embodiment, or example should be understood to be applicable to any other aspect, embodiment, or example described in this section or elsewhere in this specification, unless otherwise compatible. All features disclosed herein (including the accompanying claims, abstract, and drawings) and / or all steps of any method or process disclosed herein may be combined in any combination, except for any combination in which at least some of such features and / or steps are mutually exclusive. The protection is not limited to the details of any of the aforementioned embodiments. The protection extends to any novel features or any novel combination of features disclosed herein (including the accompanying claims, abstract, and drawings), or any novel steps or any novel combination of any method or process disclosed herein. 【0083】 Furthermore, certain features described in this disclosure in the context of separate implementations may be implemented in combination in a single implementation. Conversely, various features described in the context of a single implementation may be implemented separately or in any suitable partial combination in multiple implementations. Moreover, while features may be described above as acting in a particular combination, one or more features from a claimed combination may, in some cases, be removed from the combination, and this combination may be claimed as a partial combination or a variation of a partial combination. 【0084】 Furthermore, while operations may be shown in the drawings or described herein in a specific order, such operations do not need to be performed in the specific order shown or in a sequential order, or not all operations need to be performed, in order to achieve the desired result. Other operations not shown or described may be incorporated into exemplary methods and processes. For example, one or more additional operations may be performed before, after, simultaneously with, or in between any of the described operations. Furthermore, operations may be rearranged or rearranged in other implementations. Those skilled in the art will understand that in some embodiments, the actual steps performed in the illustrated and / or disclosed processes may differ from those shown in the drawings. Depending on the embodiment, certain steps among the steps described above may be omitted, or other steps may be added. Furthermore, the features and attributes of the particular embodiments disclosed above may be combined in different ways to form additional embodiments, all of which are within the scope of this disclosure. Also, the separation of various system components in the above implementations should not be understood as requiring such separation in all implementations, and the described components and systems may generally be integrated together in a single product or packaged in multiple products. For example, any of the components of the energy storage system described herein may be provided separately or integrated (e.g., packaged together or mounted together) to form an energy storage system. 【0085】 For the purposes of this disclosure, certain aspects, advantages, and novel features are described herein. Not all such advantages can necessarily be achieved according to any particular embodiment. Therefore, for example, a person skilled in the art will recognize that this disclosure may be embodied or implemented to achieve one advantage or group of advantages taught herein without necessarily achieving other advantages that can be taught or suggested herein. 【0086】 Conditional language such as “can,” “could,” “might,” or “may,” unless otherwise specified or understood to have a different meaning in the context in which they are used, is generally intended to convey that a particular embodiment includes certain features, elements, and / or steps, but other embodiments do not. Therefore, such conditional language does not generally imply that features, elements, and / or steps are required in any way in one or more embodiments, or that one or more embodiments necessarily include logic for determining whether these features, elements, and / or steps should be included in or performed in any particular embodiment, with or without user input or prompting. 【0087】 Conjunctions such as the phrase "at least one of X, Y, and Z" are generally understood in contexts where they are used to convey that an item, term, etc., could be any of X, Y, or Z, unless otherwise specified. Therefore, such conjunctions are not generally intended to mean that a particular embodiment requires the presence of at least one X, at least one Y, and at least one Z. 【0088】 As used herein, the terms “approximately,” “about,” “generally,” and “substantially” refer to values, quantities, or characteristics that are still close to the stated values, quantities, or characteristics that perform the desired function or achieve the desired result. 【0089】 The scope of this disclosure is not intended to be limited by any specific disclosure of embodiments in this section or elsewhere in this specification, but may be defined by the claims, as presented in this section or elsewhere in this specification, or as presented in the future. The language of the claims should be interpreted broadly on the basis of the language used in the claims, and not limited to the examples described herein or in the course of the application, and these examples should be interpreted as non-exclusive. 【0090】 While specific embodiments have been described, these embodiments are presented as examples only and are not intended to limit the scope of this disclosure. In fact, the novel methods and systems described herein can be embodied in a variety of other forms. Furthermore, various omissions, substitutions, and modifications can be made to the systems and methods described herein without departing from the spirit of this disclosure. The appended claims and their equivalents are intended to encompass forms or modifications that fall within the scope and spirit of this disclosure. Accordingly, the scope of the invention is defined solely by reference to the appended claims.

Claims

[Claim 1] It is an independent firing element, It contains at least 95% by weight of cathode active material, The self-supporting firing element includes a surface pattern 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 is 1.7 to 2.3 g / cm³ ３ It contains the density of Each of the aforementioned plurality of channels has a channel width of 5 to 100 mm, and A self-supporting firing element in which each of the plurality of channels has a channel spacing of 10 to 200 mm. [Claim 2] The self-supporting firing element according to claim 1, wherein the cathode active material comprises crystalline cathode active material particles. [Claim 3] The cathode active material is 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), LiNiO ２ A self-supporting firing element according to claim 1, selected from the group consisting of, or combinations thereof. [Claim 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. [Claim 5] The self-supporting firing element according to claim 1, wherein the self-supporting firing element substantially does not contain a binder. [Claim 6] The self-supporting firing element according to claim 1, wherein the self-supporting firing element includes a plurality of through holes. [Claim 7] The self-supporting firing element according to claim 6, wherein the self-supporting firing element includes 2 to 50 through holes. [Claim 8] The self-supporting firing element according to claim 6, wherein each of the plurality of through holes has a diameter of 10 to 30 mm. [Claim 9] The self-supporting firing element according to claim 6, wherein the self-supporting firing element includes the plurality of through holes in an area of ​​0.1 to 30% of the total element volume. [Claim 10] A self-supporting firing element according to any one of claims 1 to 9, wherein each channel has a channel width of 10 to 75 mm. [Claim 11] A self-supporting firing element according to any one of claims 1 to 9, wherein each channel has a channel spacing of 20 to 150 mm. [Claim 12] The self-supporting firing element according to any one of claims 1 to 9, wherein the self-supporting firing element is in the shape of a brick or tile. [Claim 13] The aforementioned self-supporting firing element is 1.9 to 2.3 g / cm³ ３ A self-supporting firing element according to any one of claims 1 to 9, comprising the density of the above. [Claim 14] The aforementioned self-supporting firing element is 1.7 to 1.8 g / cm³ ３ A self-supporting firing element according to any one of claims 1 to 9, comprising the density of the above. [Claim 15] 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 surface pattern 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 bounded path positioned between the first and second openings, each of the plurality of channels having a channel width of 5 to 100 mm, and each of the plurality of channels having a channel spacing of 10 to 200 mm. 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. [Claim 16] The process according to claim 15, wherein the reagent is a lithium reagent. [Claim 17] The process according to claim 16, wherein the lithium reagent is selected from the group consisting of lithium hydroxide, lithium hydroxide monohydrate, lithium carbonate, and combinations thereof. [Claim 18] The process according to claim 15, wherein the metal precursor is selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, and combinations thereof. [Claim 19] The process according to claim 15, wherein the metal precursor comprises a metal selected from the group consisting of Ni, Mn, Co, Al, Mg, Fe, Ti, and combinations thereof. [Claim 20] The process according to claim 15, wherein the solvent is water. [Claim 21] The process according to claim 15, wherein the precursor mixture contains 0.1 to 20% by weight of a solvent. [Claim 22] The process according to any one of claims 15 to 21, wherein the precursor mixture further comprises a binder. [Claim 23] The process according to claim 22, 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. [Claim 24] The process according to claim 22, wherein the precursor mixture comprises 0.025 to 1% by weight of a binder. [Claim 25] The process according to any one of claims 15 to 21, wherein the self-supporting precursor element includes a plurality of through holes. [Claim 26] The process according to any one of claims 15 to 21, further comprising the step of stacking a plurality of the self-supporting precursor elements to form an element stack. [Claim 27] The process according to claim 26, wherein the element stack includes at least one channel between adjacent independent precursor elements. [Claim 28] The aforementioned independent precursor element is present in a concentration of 1.9 to 2.3 g / cm³. ３ The process according to any one of claims 15 to 21, comprising the density of the [Claim 29] The process according to any one of claims 15 to 21, wherein the self-supporting precursor element is placed on a substrate while being heated. [Claim 30] The process according to claim 29, wherein the self-supporting precursor element is transported through a high-temperature tunnel kiln when heated. [Claim 31] The process according to any one of claims 15 to 21, 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. [Claim 32] The process according to any one of claims 15 to 21, wherein the heating is carried out at a temperature of 650 to 850°C. [Claim 33] The process according to any one of claims 15 to 21, wherein the process includes a step of preheating the self-supporting precursor element. [Claim 34] The process according to any one of claims 15 to 21, wherein the process does not include an additional heating step of the cathode active material. [Claim 35] The process according to any one of claims 15 to 21, further comprising destroying the self-supporting calcination element to form calcination element powder. [Claim 36] The process according to claim 35, wherein the destruction includes a step selected from the group consisting of crushing, grinding, and combinations thereof. [Claim 37] The process according to any one of claims 15 to 21, further comprising processing the cathode active material. [Claim 38] The process according to claim 37, wherein the processing includes a step selected from the group consisting of sieving, washing, filtering, drying, coating, and combinations thereof. [Claim 39] A process for forming a cathode electrode, A step of incorporating the cathode active material according to any one of claims 15 to 21 into an electrode film, A process comprising the step of placing the electrode film on a current collector. [Claim 40] A process for forming an energy storage device, comprising the step of arranging a separator, an anode electrode, and a cathode electrode according to claim 39 within a housing, The separator is placed between the anode electrode and the cathode electrode in the process. [Claim 41] The process according to claim 40, wherein the energy storage device is a battery.