Systems and methods for heating and / or quenching lithium-containing metal oxides

Abstract

The heat treatment system includes an inclined rotary furnace configured to sinter a powder at a sintering temperature, a quenching device configured to quench the sintered powder in a quenching fluid, and a transfer conduit configured to supply the sintered powder having a sintering temperature from the inclined rotary furnace to the quenching device in 500 milliseconds or less.

Description

[Technical Field]

[0001] Aspects of the present invention relate to a ceramic powder processing furnace and a method for forming a lithium-rich lithium nickel manganese oxide cathode active material using a ceramic powder (or powder) processing furnace. [Background technology]

[0002] Cobalt-containing cathode materials in lithium-ion batteries account for a significant portion of the cost of modern battery cells, making cobalt a major cost factor. Cobalt is a commodity with a complex and therefore volatile supply chain. For this reason, there is a need for reliable cobalt-free lithium-ion battery cathode materials. [Overview of the project] [Problems that the invention aims to solve]

[0003] Aspects of the present invention relate to a furnace for processing ceramic powders and a method for forming lithium-rich (or lithium-enriched, or lithium-high) lithium nickel manganese oxide cathode active material using the furnace for processing ceramic powders. The scope of the present invention may include, depending on the circumstances, interrelated products, alternative solutions to specific problems, and / or multiple diverse applications of one or more systems and / or articles.

[0004] According to various embodiments, the heat treatment system includes an inclined rotary furnace configured to sinter a powder at a sintering temperature, a quenching device configured to quench at least a portion of the sintered powder in a quenching fluid, and a transfer conduit configured to supply at least a portion of the sintered powder having a sintering temperature from the inclined rotary furnace to the quenching device in 500 milliseconds or less.

[0005] According to various embodiments, the method includes sintering a powder at a sintering temperature in an inclined rotary furnace, and supplying at least a portion of the sintered powder having the sintering temperature from the inclined rotary furnace to a quenching fluid in a quenching device via a transfer conduit, at least partially by gravity, in 500 milliseconds or less.

[0006] Other advantages and novel features of the present invention will become apparent from the following detailed description of various non-limiting embodiments of the invention, in conjunction with the accompanying drawings. In the event that this specification and any documents incorporated by reference contain conflicting and / or inconsistent disclosures, this specification shall prevail. [Brief explanation of the drawing]

[0007] Non-limiting embodiments of the present invention will be described illustratively with reference to the accompanying drawings, which are schematic and not intended to be drawn to scale. In the drawings, each identical or substantially identical component shown is usually represented by a single number. For clarity, not all components are referenced in each drawing, and not all components are shown in every drawing if illustration is not necessary for a person skilled in the art to understand the invention. In the drawing: [Figure 1A] Figure 1A is a schematic cross-sectional view of an example of a heat treatment system according to one embodiment. [Figure 1B] Figure 1B is a perspective view of an example of a heat treatment system according to one embodiment. [Figure 1C] Figure 1C is a schematic diagram of an example of a circulating rapid cooling system according to one embodiment. [Figure 1D] Figure 1D is a schematic diagram of an example of a circulating rapid cooling system according to one embodiment. [Figure 1E] Figure 1E is a schematic diagram of an example of a circulating rapid cooling system according to one embodiment. [Figure 2A] Figure 2A is a photograph of a rapid cooling system according to one embodiment. [Figure 2B]Figure 2B includes four consecutive video capture time-lapse images taken at 30 frames per second, illustrating a rapid quenching process according to one embodiment. [Figure 3] Figure 3 is a graph showing the X-ray diffraction (XRD) patterns of the Lix(MnyNi1-y)2-xO2 material before and after rapid cooling, when x=1.2 and y=0.75, according to one embodiment. [Figure 4] Figure 4 is a graph showing the X-ray diffraction (XRD) patterns of the Lix(MnyNi1-y)2-xO2 material before and after rapid cooling, when x=1.2 and y=0.75, according to one embodiment. [Figure 5] Figure 5 is a graph showing the X-ray diffraction pattern of the Lix(MnyNi1-y)2-xO2 material for x=1.16 and y=0.7 according to one embodiment. [Figure 6] Figure 6 is a graph showing the X-ray diffraction pattern of a Lix(MnyNi1-y)2-xO2 material treated with microwave heating and ultra-rapid quenching according to one embodiment, for x=0.116 and y=0.7. [Figure 7A] Figure 7A is a transmission electron microscope (TEM) atomic map image of an LRMO material in which rapid quenching was not performed before electrochemical cycling, according to one embodiment. [Figure 7B] Figure 7B is a TEM HAADF atomic map micrograph of an LRMO material that underwent rapid quenching before electrochemical cycling according to one embodiment. [Figure 8A] Figure 8A is a graph showing the cell potential relative capacitance according to one embodiment; [Figure 8B] Figure 8B is a graph of specific capacity versus cycles for a comparative example of Lix(MnyNi1-y)2-xO2 material when x=1.16 and y=0.7, without microwave treatment or rapid cooling (in this case, relatively slow cooling on a metal plate). [Figure 9A] Figure 9A is a graph showing the cell potential-to-capacitance ratio during the break-in cycle according to one embodiment. [Figure 9B]Figure 9B is a graph showing the cell potential-to-capacitance ratio over time. [Figure 9C] Figure 9C is a graph showing the specific capacity versus cycle at the C / 20 rate for an exemplary cell containing an LRMO active material according to one embodiment. [Figure 10A] Figure 10A is a graph showing the cell potential-to-capacitance ratio of two comparison cells containing the Lix(MnyNi1-y)2-xO2 active material in one embodiment, where x=0.12 and y=0.75 without rapid cooling. [Figure 10B] Figure 10B is a graph showing the specific volume versus cycle of the rapidly cooled material in Figure 10A. [Figure 11] Figure 11 is a chart showing the X-ray diffraction pattern results of an S-LRMO active material having formula (1): Li[Li0.14Na0.06Mn0.6Ni0.2]O2 according to one embodiment. [Figure 12] Figure 12 is a chart showing the X-ray diffraction pattern results of an S-LRMO active material having formula (1):Li[Li0.06Na0.14Mn0.6Ni0.2]O2 according to one embodiment. [Figure 13] Figure 13 is a chart showing the X-ray diffraction pattern results of an S-LRMO active material having formula (1): Li[Li0.06K0.14Mn0.6Ni0.2]O2 according to one embodiment. [Figure 14] Figure 14 is a chart showing the X-ray diffraction pattern results of an S-LRMO active material having formula (1): Li[Li0.06Na0.07K0.07Mn0.6Ni0.2]O2 according to one embodiment. [Figure 15] Figure 15 is a chart showing electrochemical data, including charge / discharge performance, of an S-LRMO material according to one embodiment. [Figure 16] Figure 16 is a chart showing electrochemical data, including charge / discharge performance, of an S-LRMO material according to one embodiment. [Figure 17] Figure 17 is a chart showing electrochemical data, including the cycle life, of an S-LRMO material according to one embodiment. [Figure 18]Figure 18 is a chart showing electrochemical data, including charge / discharge performance, of an S-LRMO material according to one embodiment. [Figure 19] Figure 19 is a chart showing electrochemical data, including efficiency as a function of cycle number, for an S-LRMO material according to one embodiment. [Figure 20] Figure 20 is a chart showing electrochemical data, including the cycle life, of an S-LRMO material according to one embodiment. [Figure 21] Figure 21 is a chart showing electrochemical data, including charge / discharge performance, of an S-LRMO material according to one embodiment. [Figure 21] Figure 21 is a chart showing electrochemical data, including charge / discharge performance, of an S-LRMO material according to one embodiment. [Figure 23] Figure 23 is a chart showing rate capability data for a potassium-substituted LRMO material according to one embodiment. [Figure 24] Figure 24 is a chart showing the data from the first two charge / discharge cycles of a lithium metal half-cell fabricated using the material Li[Li0.015[Na0.155Mn0.58Ni0.25]O2, exhibiting a specific capacity exceeding 250 mAh / g at a C / 20 rate. [Figure 25] Figure 25 is a graph showing the cycle life data of a lithium metal anode half-cell fabricated with the material Li[Li0.015[Na0.155Mn0.58Ni0.25]O2]. According to one embodiment, it exhibits stable capacity retention well over 200 mAh / g and repeated reference cycles. The median discharge voltage is also stable at the nominal value, which is not typical for lithium-rich cathode materials. [Modes for carrying out the invention]

[0008] Aspects of this disclosure relate to a heat treatment system configured to heat and quench a powder (e.g., a cathode active material powder). In the context of this disclosure, certain configurations of the heat treatment system, such as having a furnace configured to sinter the powder while stirring it, have been realized that provide a favorable thermal profile to each fine particle of the powder, and that the powder can then be rapidly quenched. The heat treatment system can be configured to deliver the sintered powder from the furnace to a quencher while the temperature of the sintered powder is still relatively high (e.g., below 200 degrees Celsius), which can provide a favorable quench compared to certain existing systems (e.g., those in which the powder is significantly cooled before being removed from the furnace).

[0009] In some embodiments, though not necessarily in all, the powder introduced into the heat treatment system includes a lithium-rich metal oxide (LRMO). Various embodiments provide a rapid and inexpensive method for forming crystallographically stable, durable, and cobalt-free (or cobalt-free) lithium-rich metal oxide (LRMO) material. In some embodiments, the LRMO material is a lithium-rich lithium manganese nickel oxide material represented by the following formula 1: Li x (Mn y Ni 1-y ) 2-x O2(1) (In the formula, x is greater than 1.0 and less than 1.25, and y is between 0.95 and 0.1, for example, y is between 0.5 and 0.8.)

[0010] In some embodiments, the LRMO material is a lithium-rich lithium manganese nickel oxide represented by the following formula 2: Li[Li (1 / 3-2x / 3) Mn (2 / 3-x / 3) Ni x ]O2(2) (In the equation, x is between 0.1 and 0.4, inclusive.)

[0011] In the original state (e.g., before the first charge), the LRMO material may have a hexagonal (e.g., rhombohedral) phase and a monoclinic phase that are distinct in some embodiments. Thus, in some embodiments, the LRMO material may instead be represented by the formula: (1-x)[Li2MnO3] * x[LiMn a Ni (1-a) O2], where the first part of this formula represents the relative molar amount (1-x) of the monoclinic phase and the second part of this formula represents the relative molar amount (x) of the rhombohedral phase. In some embodiments, the molar fraction "x" of the rhombohedral phase is generally in the range of 0.8 or more and 0.95 or less, and "a" is 0.6 or more and 0.9 or less. In some embodiments, the two phases may be arranged in a layered structure.

[0012] Various embodiments can provide an LRMO material that exhibits a high (e.g., >240 mAh / g) specific capacity and a high functional voltage window (e.g., 2.0 V or more and 4.8 V or less) when used as a cobalt-free (or cobalt-free) cathode active material.

[0013] According to various embodiments, the method of forming the LRMO material includes rapid heat treatment and rapid (e.g., less than 10 seconds) or ultra-rapid (e.g., less than 500 milliseconds) quenching that results in an LRMO material having an excellent crystal structure with the desired atomic order / disorder. These features may unexpectedly result in strong long-term stability and performance when used as a cathode active material.

[0014] Some LRMO materials (e.g., those synthesized without rapid quenching and / or quenching in water) may be unsuitable for use as cathode active materials due to low rate capability and / or low capacity retention, which are thought to be caused by factors such as structural instability due to oxygen loss, migration of transition metal ions during use, and / or the possibility of manganese dissolution. While we do not wish to be bound by any particular theory, two of the most common aging degradation mechanisms are a decrease in average discharge voltage as the material slowly reorganizes into a predominantly spinel structure, and capacity loss during cycling due to mechanical and / or chemical degradation of the material.

[0015] Thermal decomposition and processing LRMO materials can be synthesized from precursor materials using various methods. Table 1 below lists specific methods that can be used for synthesizing LRMO materials, including precursor synthesis, precursor materials, quenching methods, performance evaluation criteria, and the discharge capacity (DC) of the LRMO material cathode.

[0016] [Table 1] JPEG2026513621000002.jpg213169

[0017] As shown in Table 1, the three main synthesis routes for LRMO materials are combustion following sedimentation, hydrothermal synthesis, intermediate thermal decomposition following sol-gel solution production, and high-temperature heat treatment (calcination, annealing, sintering, etc.).

[0018] As shown in Table 1, the number of studies investigating the effect of nickel composition on the performance of LRMO cathodes has decreased over time, and multiple nickel compositions or formulas:Li[Ni x Li (1 / 3-2x / 3) Mn (2 / 3-x / 3)Few studies have investigated nickel compositions less than x=0.2 in cathodes containing ]O2. Table 1 also shows significant inconsistencies in the synthesis routes employed throughout the studies. Furthermore, few studies have conducted detailed comparative evaluations of the influence of synthesis methods on the performance of LRMO cathodes. In LRMO materials, the order and disorder of transition metals are important, and both composition and synthesis techniques may provide mechanisms that influence the degree of structural order and disorder. The electrochemical behavior resulting from these compositional and synthetic variations, such as differences in defect concentration, can have a significant impact on the properties of LRMO cathodes.

[0019] While we do not wish to be bound by any particular theory, it is believed that when a sample is rapidly cooled in liquid nitrogen, the particles are immediately shielded by an adiabatic envelopment of nitrogen gas similar to the Leidenfrost effect, significantly reducing the heat transfer coefficient. In the preparation of certain conventional cathode materials, it is believed that lithium-containing cathode materials for lithium-ion batteries should not come into contact with moisture, because moisture leaches lithium from such cathode materials and forms a lithium hydroxide coating on the material. Furthermore, in lithium-ion batteries containing lithium iron phosphate as the cathode material, it is known that water can cause failure of the lithium-ion battery.

[0020] While we do not wish to be bound by any particular theory, we believe that relatively slow conventional quenching and cooling methods lead to the aggregation of metal oxides, thereby forming segregated nickel oxide and lithium manganese oxide phases. In particular, the nickel oxide phase can concentrate on the surface of LRMO material particles (e.g., crystallites). While we do not wish to be bound by any particular theory, this aggregation of surface nickel oxide, and the segregation of nickel and manganese in the general crystal structure, may be at least partially responsible for the chemical instability of conventional LRMO active materials.

[0021] In contrast, the inventors unexpectedly discovered that rapid cooling with water does not adversely affect the LRMO cathode and does not cause lithium leaching from such LRMO cathodes. An example of an embodiment of rapid cooling with water using unsubstituted LRMO is described in U.S. Patent Application No. 17 / 810 / 722, filed on 5 July 2022, and published on 19 January 2023, U.S. Patent Publication No. 2023 / 0015455, entitled "Lithium-Rich Nickel Manganese Oxide Battery Cathode Materials and Methods," which is incorporated herein by reference in its entirety for all purposes. Rapid cooling with water is thought to increase the heat transfer coefficient by causing vaporization in the form of bubble nucleation and dissipation. Thus, even without wishing to be bound by theory, rapid cooling with water is generally thought to have a heat transfer coefficient approximately two orders of magnitude higher than rapid cooling with liquid nitrogen. Furthermore, in some cases, both water and the additives dissolved in it (i.e., other materials that may be dissolved in water) may react when the high-temperature LRMO is quenched to form advantageous surface terminations and / or coatings that enhance electrochemical stability and durability when used in lithium-ion batteries. As will be described in more detail below, the methods, conditions, parameters, and / or processing steps described above can be applied in some embodiments to the substituted LRMO materials described herein.

[0022] Furthermore, in many of the rapid cooling pathways described above in the context of Table 1, rapid cooling is performed on press-sintered or partially-sintered pellets of material that remain as larger bodies (e.g., having widths on the order of centimeters). In contrast, in some embodiments of the present disclosure, rapid cooling is performed on loose powders and / or ground powders having particles that are aggregates with an average diameter of 20 microns or less, e.g., 0.1 to 20 microns, e.g., 0.1 to 1 micron, or 1 to 20 microns, such that when the particles come into contact with a rapid cooling liquid (e.g., water), the entire material cools rapidly and at approximately the same rate. Other ranges are also possible. Each aggregate may consist of crystallites having an average size of 25 nm to 500 nm, e.g., 50 nm to 200 nm. Other ranges are also possible. Each crystallite may include a single crystal of LRMO material. The crystallites may be partially fused or completely fused within the aggregate. When crystallites are completely melted within an aggregate (i.e., within powder particles), each crystallite contains a single crystal grain of the powder particle and is separated from other single crystal grains within the same powder particle by grain boundaries. The average crystal grain size of the powder particles can be between 25 nm and 500 nm, for example, between 50 nm and 200 nm. Other ranges are also possible. The aggregate is relatively porous, allowing water to reach the crystallites within the aggregate.

[0023] While some embodiments described herein generally refer to sintered or partially sintered particles, those skilled in the art will understand, based on the teachings herein, that the particles are not necessarily fused (e.g., loose particles and / or pulverized particles). In some embodiments, the particles are heated to a temperature suitable for sintering (e.g., sintering temperatures described herein), but this does not necessarily result in fusion between the particles. For example, without wishing to be constrained by theory, in some embodiments, the particles are heated to a temperature suitable for promoting a relatively high degree of atomic disorder in the particle material. In some embodiments, heating the particles increases the entropy of the powder material.

[0024] In some embodiments, the material subjected to rapid cooling (e.g., LRMO or S-LRMO described later) comprises a powder containing particles (e.g., loose particles) having an average maximum cross-sectional dimension of 20 microns or less, 10 microns or less, 5 microns or less, 2 microns or less, or less. In some embodiments, the material subjected to rapid cooling (e.g., LRMO or S-LRMO described later) comprises a powder containing particles (e.g., loose particles) having an average maximum cross-sectional dimension of 0.1 microns or more, 0.2 microns or more, 0.5 microns or more, 1 micron or more, or more. As described above, combinations of these ranges are also possible. Other ranges are also possible. In some embodiments, the material subjected to rapid cooling (e.g., LRMO or S-LRMO described later) comprises a powder containing particles (e.g., loose particles) containing aggregates of crystallites having an average maximum cross-sectional dimension of 25 nm or more, 50 nm or more, or 100 nm or more. In some embodiments, the material subjected to rapid cooling (e.g., LRMO or S-LRMO described later) comprises a powder containing particles (e.g., loose particles) that include aggregates of crystallites having an average maximum cross-sectional dimension of 500 nm or less, 300 nm or less, 200 nm or less, or less. Combinations of these ranges are also possible. Other ranges are also possible. The average maximum cross-sectional dimension of the particles and / or crystals can be determined, for example, by transmission electron microscopy.

[0025] Advantageously, in some embodiments, at least a portion of the particles (at least 10%, at least 30%, at least 50%, at least 70%, at least 90%, at least 95%, at least 98%, at least 99%) undergo relatively similar temperature changes over time. That is, in some embodiments, the quenching apparatus and / or system described herein provides a uniform rate of temperature change to at least a portion of the particles during quenching.

[0026] Rapid and ultra-rapid quenching According to various embodiments, LRMO cathode active materials can be formed by heat treatment (e.g., sintering, firing, and / or annealing) and quenching of LRMO material powder. In particular, the heat treatment may include high-temperature treatment (or process) in which the LRMO material is heated to a sintering temperature of 800°C to 1000°C, for example, 850°C to 950°C, or 900°C or less. Other ranges are also possible. The heat treatment can be carried out in any suitable heat treatment apparatus, such as a tubular furnace, muffle box furnace, rotary hearth furnace, belt furnace, etc. In some embodiments, as will be described in more detail below, the furnace is configured to agitate (or mix) the powder (e.g., LRMO material powder) for at least part of the heat treatment (e.g., during sintering). In some embodiments, the heat treatment may optionally include one or more low-temperature precursor decomposition (e.g., firing) treatments in which the LRMO material is heated to a temperature above room temperature but below 800°C. For example, firing may include heating the LRMO material to a temperature between 450°C and 550°C, for example, 500°C, before high-temperature processing. Other temperature ranges are also possible.

[0027] According to various embodiments, the quenching process may include transferring the heated LRMO material to a quenching bath. The quenching bath may be part of the quenching fluid in the quenching apparatus described herein. For example, the LRMO material may be dropped directly from the heat treatment apparatus into the quenching bath. As will be described in more detail below, the methods, conditions, parameters, and / or processing steps described above may be applied to the substituted LRMO material described herein in some embodiments.

[0028] In some existing methods, the LRMO material may be cooled slowly while it is being moved from the furnace. For example, the transfer process can take up to 10 seconds, during which time the temperature of the LRMO material decreases slowly. The inventors have determined that slow cooling before entering the rapid cooling bath may lead to undesirable changes in the crystal structure of the LRMO sintered body. In other words, the temperature at which the sintered LRMO material enters the rapid cooling bath may be important for providing the desired crystal structure. For example, slow cooling may result in a less desirable crystal structure.

[0029] According to various embodiments, the transfer process can be configured such that the sintered LRMO material enters a rapid cooling bath after sintering at a temperature of at least 800°C, such as 800°C to 950°C, 850°C to 925°C, or 900°C. For example, the transfer time from the heat treatment apparatus to the rapid cooling bath can be limited to 10 seconds or less, e.g., 1 second or less, e.g., 0.5 seconds or less, or 0.2 seconds or less. Thus, the sintered LRMO material is cooled from the heat treatment temperature (e.g., a sintering temperature of at least 800°C, e.g., 800°C to 950°C, 850°C to 925°C, or 900°C) in 10 seconds or less, e.g., 0.5 seconds or less, including 0.2 seconds or less. Other ranges are also possible. In this specification, the "ultra-rapid quenching process" may have a cooling time of 0.5 seconds or less, for example, 0.2 seconds or less, for example, 0.1 seconds or more and 0.2 seconds or less, and the "quenching process" may have a cooling time of 10 seconds or less, for example, 0.5 seconds or more and 10 seconds or less. Other ranges are also possible.

[0030] Sintered LRMO powder particles can be rapidly cooled in a quenching bath at an average rate of at least 50°C / second, for example, at least 50°C / second and no more than 10,000°C / second. For example, sintered LRMO powder particles can be rapidly cooled at rates including 87.5°C / second to 8750°C / second, for example, 1750°C / second to 8750°C / second, for example, 4375°C / second to 8750°C / second. Other ranges are also possible. Thus, sintered LRMO material can be rapidly cooled from a temperature between a heat treatment temperature of at least 800°C (e.g., sintering temperature) and the temperature of the quenching bath (e.g., a water bath at room temperature of 25°C) for 10 seconds or less, for example, 500 milliseconds or less, including 400 milliseconds or less, 300 milliseconds or less, or 200 milliseconds or less. For example, rapid cooling can occur with time periods of 100 milliseconds or less, 400 milliseconds or less, or 100 milliseconds or more and 200 milliseconds or less. Other ranges are also possible. As will be described in more detail below, the methods, conditions, parameters, and / or processing steps described above can be applied in some embodiments to the substituted LRMO materials described herein.

[0031] In some embodiments, the LRMO material (or S-LRMO material) is rapidly cooled from the sintering temperature (e.g., at least 800°C, such as 800°C to 1000°C, or above 850°C and below 950°C) to a rapid cooling temperature within the range of 10°C to 15°C, 20°C, and / or 120°C or below, 100°C or below, 80°C or below, 60°C or below, 50°C or below, 45°C or below, 40°C or below, 35°C or below, 30°C or below, and 25°C or below. In some embodiments, the rapid cooling temperature is room temperature (e.g., 25°C). Rapid cooling can occur in 500 milliseconds or less, 400 milliseconds or less, 300 milliseconds or less, 200 milliseconds or less, and / or 150 milliseconds or less, 100 milliseconds or less, or less. Combinations of these ranges (e.g., rapid cooling occurring in periods of 100 milliseconds to 500 milliseconds, or 100 milliseconds to 200 milliseconds) are also possible. Other ranges are also possible.

[0032] In some embodiments, quenching (for example, within the period described above) includes bringing at least 25% by weight, at least 50% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight, at least 98% by weight, at least 99% by weight, at least 99.9% by weight or more (e.g., 100% by weight) of the sintered LRMO material (or S-LRMO material) to thermal equilibrium (e.g., in combination with an ambient medium such as a quenching bath), where the temperature is 10°C or higher, 15°C or higher, 20°C or higher, and / or 120°C or lower, 100°C or lower, 80°C or lower, 60°C or lower, 50°C or lower, 45°C or lower, 40°C or lower, 35°C or lower, 30°C or lower, 25°C or lower (e.g., within the range of room temperature (e.g., 25°C)). Cooling involves bringing at least 25 vol%, at least 50 vol%, at least 80 vol%, at least 90 vol%, at least 95 vol%, at least 98 vol%, at least 99 vol%, at least 99.9 vol%, or more (e.g., 100 vol%) of sintered LRMO material (or S-LRMO material) to thermal equilibrium (e.g., in conjunction with an ambient medium such as a quenching bath), where the temperature is in the range of 10°C or higher, 15°C or higher, 20°C or higher, and / or 120°C or lower, and is 100°C or lower, 80°C or lower, 60°C or lower, 50°C or lower, 45°C or lower, 40°C or lower, 35°C or lower, 30°C or lower, 25°C or lower, or lower (e.g., within the range of room temperature (e.g., 25°C). Other ranges are also possible).

[0033] The quenched fluid may contain oil, alcohol, or water, and may optionally contain additives. For example, the quenched fluid may be an oil bath, an alcohol bath, or a water bath. The quenched fluid is also called a quenched bath. The quenched fluid or quenched bath may contain 50% or more by weight of water, 80% or more by weight of water, 90% or more by weight of water, 95% or more by weight of water, 98% or more by weight of water, 99% or more by weight of water, or more (e.g., 100% by weight). Other ranges are also possible. The quenched fluid or quenched bath may contain one or more additives, such as at least one acid or at least one carbohydrate (e.g., urea or sugar), or a combination thereof, as described above. In some embodiments, the quenched fluid or quenched bath has a basic pH (e.g., pH greater than 7, 8 or greater, 9 or greater, 10 or greater, 11 or greater, 12 or greater, 14 or greater, or higher). In some embodiments, the quenched fluid or bath contains a base as an additive, such as LiOH, NaOH, and / or KOH.

[0034] The quenching bath can consist of a high-heat-capacity liquid solvent with a vaporization temperature of less than 200°C. For example, the quenching bath may include solvents such as water, oil, and / or alcohol. In some embodiments, the quenching bath may include additives configured to modify the surface of the LRMO material during quenching and improve the long-term chemical stability of the material. The additives may include acids, bases, alcohols, and / or dissolved carbon species, for example, acids, alcohols, or carbon species dissolved in water (e.g., urea).

[0035] For example, the quenching bath can be an aqueous quenching fluid containing an aqueous solution of an acid additive in a concentration of 0.01 mol / L to 1.0 mol / L, for example, 0.1 mol / L to 1.0 mol / L, or 0.5 mol / L to 1.0 mol / L, such as sulfuric acid, hydrochloric acid, nitric acid, oxalic acid, citric acid, acetic acid, phosphoric acid, orthophosphoric acid, lithium hydroxide, sodium hydroxide, potassium hydroxide, or a combination thereof. Other ranges are also possible. The acid can be configured to stabilize the surface of the LRMO particles by reacting with and / or passivating the dangling bonds and / or OH-terminal groups of the LRMO powder particles being quenched in the water containing the acid additive.

[0036] In some embodiments, acid quenching may cause the formation of a spinel structure (e.g., a surface layer) on the surface of the rapidly cooled LRMO powder particles. The spinel structure may stabilize the particles and form a framework that provides a three-dimensional pathway for lithium diffusion. In particular, it is thought that the Li ions in the particles are exchanged with the H ions of the acid, followed by a structural change on the particle surface, leading to the formation of the spinel surface layer.

[0037] In another embodiment, the quenching solution may contain alcohol and / or carbohydrate additives in addition to, or instead of, the acid additive. For example, the alcohol may be isopropyl alcohol or other alcohols, and the carbohydrate may be urea or sugar, such as fructose, galactose glucose, lactose, maltose, sucrose, or combinations thereof. In some embodiments, the quenching solution may contain a carbohydrate additive in a concentration of 0.01 mol / L to 1.0 mol / L, for example, 0.1 mol / L to 1.0 mol / L, or 0.5 mol / L to 1.0 mol / L. Other ranges are also possible. In some embodiments, the carbohydrate forms an intimate amorphous carbon coating on the surface of the LRMO powder particles during the quenching process in water containing the carbohydrate particles. While not wishing to be bound by any particular theory, the carbon coating may be advantageously permeable to Li ions but impermeable to the electrolyte of the Li-ion battery. The carbon coating may also allow volume changes to occur in the LRMO crystallites during battery charging and discharging. As will be described in more detail below, the methods, conditions, parameters, and / or processing steps described above can be applied in some embodiments to the substituted LRMO materials described herein.

[0038] Rapid or ultra-rapid quenching can yield quenched LRMO materials with crystalline structures that offer unexpected robustness and electrical properties. Specifically, the degree of crystalline order of quenched LRMO materials produced by rapid quenching (e.g., lithium-rich lithium nickel manganese oxide) can provide performance characteristics suitable for use as cathode active materials in lithium-ion batteries, offering energy density and charge / storage stability similar to cobalt-containing, high-nickel-containing, and active-material-containing cathodes.

[0039] Rapid cooling can potentially yield rapidly cooled LRMO material powders having a desired crystalline structure and particle size. For example, the rapidly cooled LRMO sintered body may be a loose powder with an average particle size of less than 1 μm, e.g., between 0.02 μm and 1 μm, or between 0.05 μm and 0.5 μm. Other ranges are also possible. In some embodiments, the rapidly cooled LRMO material may contain a crystalline phase and / or crystallites having an average crystal size of between 25 nm and 500 nm, e.g., between 50 nm and 300 nm. Each powder particle may contain one crystallite or more than one. The loosely sintered and rapidly cooled powder particles can be incorporated into a binder (e.g., a carbon binder) to form cathode electrodes for lithium-ion batteries. Other ranges are also possible.

[0040] In some embodiments, the sintered and / or quenched LRMO material (or the sintered and / or quenched S-LRMO material described below) comprises a loose powder containing particles having an average maximum cross-sectional dimension of 1 micron or less, 0.5 microns or less, 0.5 microns or less, or smaller. In some embodiments, the sintered and / or quenched LRMO material (or the S-LRMO material described below) is a loose powder containing particles having an average maximum cross-sectional dimension of 0.02 microns or more, 0.05 microns or more, 0.1 microns or more, 0.2 microns or more, or larger. Combinations of these ranges (e.g., 0.02 microns to 1 micron, or 0.05 microns to 0.5 microns) are also possible. Other ranges are also possible.

[0041] In some embodiments, the sintered and / or quenched LRMO material (or the sintered and / or quenched S-LRMO material described below) includes a loose powder containing particles having a crystalline phase and / or crystallites having an average maximum cross-sectional dimension of 500 nm or less, 300 nm or less, 200 nm or less, or less. In some embodiments, the sintered and / or quenched LRMO material (or the sintered and / or quenched S-LRMO material described below) includes a loose powder containing particles having a crystalline phase and / or crystallites having an average maximum cross-sectional dimension of 25 nm or more, 50 nm or more, 100 nm or more, 150 nm or more, or greater. Combinations of these ranges (e.g., 25 nm to 500 nm, 50 nm to 300 nm) are also possible. Other ranges are also possible.

[0042] The quenched LRMO material is dried to form an LRMO active material (e.g., heat-treated and quenched loose powder particles), which has a hexagonal primary phase and a monoclinic secondary phase. Thus, according to some embodiments, the ratio of the hexagonal phase content to the monoclinic phase content is greater than 1 and at least equal to 2, for example, at least 2 and 20 or less. For example, the sintered and quenched LRMO material (e.g., dried active material) may have a superlattice structure containing hexagonal primary phase layers separated by interlayers of monoclinic secondary phases. Alternatively, the sintered and quenched LRMO material may contain a hexagonal phase matrix containing monoclinic nanozones (i.e., regions with a width of less than a micron). Mn and Ni can be homogeneously distributed within the crystal structure of the LRMO material (e.g., excess Mn, Ni, and Li can be homogeneously and uniformly distributed on transition metal crystal lattice sites). For example, crystalline grains of sintered and quenched LRMO material may exhibit a uniform distribution of Mn and Ni atoms throughout the grain, such that there are no Ni-rich (or Ni-enriched, or Ni-heavy) or Mn-rich (or Mn-enriched, or Mn-heavy) regions when imaged by high-angle annular dark-field (HAADF) energy-dispersive X-ray spectroscopy (EDS) (i.e., in the EDS elemental map of the HAADF tunneling electron microscope image). In one embodiment, the phrase "no Ni-rich or Mn-rich regions in the crystalline grain" means that there are no crystal volumes exceeding 3 × 3 × 3 nm in a crystalline grain where the difference between the ratio of Ni atoms and the ratio of Mn atoms exceeds 3% compared to the average ratio of Ni atoms to Mn atoms in the crystalline grain as a whole.

[0043] The crystal structure of the formed activated LRMO material may change due to electrochemical cycling. For example, if the activated LRMO material is included as the active material in an electrochemical cell, the monoclinic phase may no longer be present at a detectable level after the first charge-discharge cycle. The monoclinic phase is thought to be consumed during the insertion and / or extraction of Li ions. As will be described in more detail below, the methods, conditions, parameters, and / or processing steps described above can be applied to the substituted LRMO materials described herein in some embodiments.

[0044] Heat treatment system In one embodiment, a system for heating a material (e.g., ceramics such as lithium-containing metal oxides) is provided. In some embodiments, the system includes a furnace. In some embodiments, the furnace is configured such that the material (e.g., ceramics such as lithium-containing metal oxides (including the above-mentioned LRMO)) can be heat-treated continuously within the furnace (as opposed to, for example, being processed in a batch or semi-batch manner). In some embodiments, the system is a heat treatment system configured to sinter a powder (e.g., a material such as LRMO material or S-LRMO material) at a sintering temperature.

[0045] Figure 1A is a schematic cross-sectional view of a heat treatment system 100 according to several embodiments. Although the heat treatment system 100 is shown in Figure 1A as including a furnace 110 connected to a quenching device 150 via a transfer conduit 140, it should be understood that any of various configurations are possible, and in some embodiments, one or more components of the system 100 may be replaced by different components or may not be present. In some embodiments, the material powder to be treated enters the furnace 110 at an inlet (e.g., indicated by arrow 111 in Figure 111). The system 100 may be configured so that at least a portion of the material powder to be treated (e.g., heated at sintering temperature) is rapidly transferred from the furnace 110 to the quenching device 150 (e.g., in the direction indicated by arrow 112 in Figure 1A).

[0046] Figure 1B is a perspective view of the heat treatment system 100 according to several embodiments. Referring to Figures 1A-1B, the system 100 may be configured to continuously heat-treat (e.g., heat and quench) a treatment material powder, such as a ceramic material powder like the LRMO material powder described above.

[0047] In some embodiments, the furnace is a rotary furnace (e.g., a rotary tube furnace). For example, in the embodiment shown in Figure 1B, system 100 includes a furnace 110 which is a rotary furnace. Such a furnace can facilitate agitation of at least a portion of the powder being processed (e.g., by rotation of at least a portion of the furnace), thereby potentially causing agitation forces (a combination of torque and gravity) to act on that portion of the powder. In some embodiments, the furnace is configured to transport at least a portion of the powder being processed (e.g., to the furnace outlet port). In some embodiments, the furnace outlet port is positioned such that the heated powder particles exit the furnace at the heating temperature (e.g., sintering temperature) before coming into contact with a quenching liquid. For example, in some embodiments, the outlet port is in fluid communication with the quenching liquid. In some embodiments, the outlet port is located within the high-temperature zone of the furnace. In the context of this disclosure, it is evident that agitating at least a portion of the powder during at least a portion (or all) of the time during which heating (e.g., sintering) is performed can be advantageous in that it may cause the powder particles to receive a consistent thermal profile during heating (e.g., by mixing the particles over time). Promoting particle agitation and / or ensuring each particle receives essentially the same thermal profile is in contrast to typical heating techniques for electrode materials, which tend to use static ovens, where parts of the material inside a mass may receive different temperatures and / or heating times than parts outside the mass. Agitation and / or a consistent thermal profile (and potentially the quenching method described throughout) can, in some embodiments, facilitate improved scalability and reliability of the manufacturing process. For example, such a dynamic heating environment may contribute to more homogeneous contact between powder particles and heat (e.g., using a high-temperature gas, such as high-temperature air containing oxygen) compared to certain existing system configurations (e.g., static furnaces).

[0048] A furnace can be configured to perform other forms of agitation in addition to, or instead of, rotation. For example, a furnace can be configured to agitate powder by vibration. Another example is that a furnace can be configured to agitate powder by forming a fluidized bed of powder. For example, a furnace can consist of a vessel and a fluid inlet, the fluid inlet being configured to introduce a fluid (e.g., gas and / or liquid) into the vessel, and the fluid (e.g., pressurized by a pump) passing through the powder can cause the powder particles to behave as a fluid (e.g., by rising in a suspended state).

[0049] A furnace (e.g., a rotary furnace) can be fluidly connected to a quenching device (e.g., via a transfer conduit). For example, referring again to the embodiment shown in Figure 1A-1B, the system 100 includes a rotary furnace 110, a transfer conduit 140, and a quenching device 150. The furnace 110 may be configured to heat at least a portion (e.g., at least 50% by weight, at least 75% by weight, at least 90% by weight, at least 95% by weight, at least 99% by weight, or all) of a material (e.g., a ceramic material such as LRMO material (or S-LRMO)) to a sintering temperature to form a sintered material (e.g., a sintered ceramic material such as a sintered LRMO material (or S-LRMO sintered body)). For example, the rotary furnace 110 can be configured to heat at least a portion (e.g., at least 50% by weight, at least 75% by weight, at least 90% by weight, at least 95% by weight, at least 99% by weight, or all) of a material (e.g., a ceramic material such as LRMO) to a sintering temperature to form a sintered material (e.g., a ceramic sintered body such as an LRMO sintered body). The heating (e.g., sintering) is carried out while the material is conveyed so as to pass through at least a portion (or all) of the furnace. For example, in Figure 1B, the material may be heated while being conveyed through the furnace 110 in the direction indicated by the horizontal arrow in Figure 1B.

[0050] The sintering temperature can be any of a variety of values, depending, for example, on the chemical composition and / or the physical form of the material (e.g., loose powder vs. large solid). In some embodiments, the sintering temperature is 800°C or higher. In some embodiments, the sintering temperature is 850°C or higher, 875°C or higher, 900°C or higher, or higher. In some embodiments, the sintering temperature is 1000°C or lower, 975°C or lower, 950°C or lower, 925°C or lower, 900°C or lower, or lower. Combinations of these ranges (e.g., 850°C to 1000°C, 850°C to 925°C, 850°C to 900°C) are also possible. In some embodiments, the furnace has multiple temperature zones. By including multiple temperature zones, the furnace can be configured to gradually increase the temperature of the material (e.g., ceramics such as LRMO) up to the sintering temperature.

[0051] In some embodiments, the system is configured to maintain at least a portion of the heated material (e.g., a ceramic such as LRMO) at or near the sintering temperature until the heated material reaches a quenching device. For example, in the embodiment shown in Figure 1B, system 100 can be configured to maintain the heated LRMO material at or near the sintering temperature until the LRMO material reaches the quenching device 150 and is quenched. For example, system 100 can be configured so that at least a portion of the heated LRMO material is supplied from furnace 100 to quenching device 150 at a temperature of at least 800°C. In a more specific example, system 100 can be configured so that at least a portion of the heated powder (e.g., LRMO or S-LRMO material) exits transfer conduit 140 (e.g., enters quenching device 150) at a temperature within 200°C of the sintering temperature (e.g., within 100°C, 75°C, 50°C, 25°C, 10°C, 5°C, 1°C, or less). In some embodiments, the system 100 is configured such that at least a portion of the heated powder (e.g., LRMO or S-LRMO material) exits the transfer conduit 140 (e.g., enters a quenching device 150) at a temperature of at least 800°C, at least 825°C, or higher. In the context of this disclosure, it has been realized that a heat treatment system that can supply powder from a heating furnace to a quenching device while relatively little (or no) of the heated powder is cooled can improve the quenching effect and provide powder having advantageous properties (such as a favorable crystal structure and / or ion distribution).

[0052] In some embodiments, the furnace is a rotary furnace. For example, the furnace is of the rotary kiln type. For example, as shown in Figure 1B, the furnace 110 includes a drum (e.g., shell) 120, a process conduit 122, a support base 130, and a drive motor 138. The drum 120 may be a high-temperature resistant material cylinder configured to heat the process conduit 122. For example, the drum 120 may include a gas burner or an electric (i.e., resistive) heating element. The process conduit 122 may include a tube (e.g., a cylindrical tube) configured to rotate about its longitudinal axis during operation of the furnace 110. The process conduit 122 may have a first end or inlet 122A, an opposing second end 122B, and one or more outlets 124. The inlet 122A may be configured to receive powdered material, such as LRMO material powder, from a material source or feeder. In some embodiments, the system includes a continuous material feeder (not shown), such as a screw feeder, configured to supply a steady supply of the material to be heated to the furnace inlet (for example, a steady supply of LRMO material to inlet 122A). Similar process conduits may also be present in furnaces of other configurations, such as furnaces configured to agitate the powder using techniques other than rotation, or in addition to rotation, such as powder vibration and / or fluidization.

[0053] In some embodiments, though not necessarily in all, the second end (e.g., second end 122B) is sealed (e.g., capped). The outlet can be located at any of several positions along the furnace process conduit, at a distance from the furnace inlet. For example, in Figure 1B, the outlet 124 may be located adjacent to the second end 122B. The outlet (e.g., outlet 124) may be a through-hole in the side wall of a process conduit (e.g., process conduit 122) extending through the side wall of the outer portion of the furnace (e.g., drum 120). For example, in Figure 1B, the outlets 124 may be arranged in an annular pattern around the surface of the process conduit 122.

[0054] In some embodiments where the furnace is a rotary furnace (e.g., a rotary kiln), the process conduit (and possibly the drum) can be rotated. Rotating the process conduit facilitates the continuous mixing and transport of the material through the conduit (e.g., as loose powder). For example, in Figure 1B, the process conduit 122 and possibly the drum 120 can be rotated so that ceramic material, such as LRMO material, supplied to the process conduit 122 is continuously mixed and transported from the inlet 122A to the outlet 124. The outlet 124 can be configured so that the LRMO material falls into the transfer conduit 140 and is not transported beyond the outlet 124 toward the second end 122B of the process conduit 122.

[0055] In some embodiments, at least part (or all) of the furnace process conduits are at a non-zero angle with respect to the horizontal. In this way, at least part of the furnace can be inclined. In some embodiments, at least part (or all) of the furnace process conduits are at an angle of 3 degrees or more, 5 degrees or more, 10 degrees or more, 15 degrees or more, or greater with respect to the horizontal. In some embodiments, at least part (or all) of the furnace process conduits are at an angle of 30 degrees or less, 25 degrees or less, 20 degrees or less, or less with respect to the horizontal. Combinations of these ranges (e.g., 3 degrees to 30 degrees, 5 degrees to 20 degrees) are also possible. In some embodiments, the horizontal direction corresponds to the direction of the surface (e.g., the floor / ground on which the heat treatment system is located).

[0056] For example, in Figure 1B, the support base 130 can be configured to support the drum 120 and the process conduit 122 at a non-zero angle with respect to the horizontal. For example, the T-base 130 may include a lower support 132 and an upper support 134 which may be positioned at a non-zero angle with respect to the lower support 132. The upper support 134 can support the drive motor 138 and the drum 120. In particular, the upper support 134 may include a gimbal 136 configured to rotatably support the process conduit. The drive motor 138 can be configured to rotate the drum 120, thereby rotating the process conduit 122.

[0057] As described above, the upper support 134 may be connected to the lower support 132 at a non-zero angle such that the process conduit 122 has a negative slope from the inlet 122A to the outlet 124. In some embodiments, the upper support 134 may be adjustably connected to the lower support 132 to control the slope of the process conduit 122 by adjusting the angle between the lower support 132 and the upper support 134. In other words, by adjusting the position of the upper support 134 relative to the lower support 132, the first end 122A of the process conduit 122 can be positioned above the outlet 124. In some embodiments, the angle formed between the lower support 132 and the upper support 134 is 3 degrees or more, 5 degrees or more, 10 degrees or more, 15 degrees or more, or greater. In some embodiments, the angle formed between the lower support 132 and the upper support 134 is 30 degrees or less, 25 degrees or less, 20 degrees or less, or less. Combinations of these ranges (for example, 3 degrees to 30 degrees, 5 degrees to 20 degrees) are also possible. Thus, the process conduit 122 can be tilted horizontally at a non-zero angle of 3 to 30 degrees, for example, 5 to 20 degrees, such that the first end 122A is higher than the second end 122B. Alternatively, the upper support 134 can also be fixed to the lower support 132 at a set angle.

[0058] The inclination and / or rotational speed of the process conduit can be controlled to control the speed at which the material (e.g., ceramic powder such as LRMO material powder) is conveyed through the furnace. For example, the inclination and / or rotational speed of the process conduit 122 can be controlled to control the speed at which the ceramic powder, such as LRMO material powder, is conveyed through the furnace 110. In this way, the material (e.g., ceramic powder such as LRMO material powder) can be uniformly mixed and heated as it moves through the process conduit 122 to the outlet 124 (e.g., at a set speed).

[0059] In some embodiments, the process conduit is fluidly connected to the quencher (e.g., via a transfer conduit). For example, referring again to the embodiment in Figure 1B, a transfer conduit 140 can fluidly connect the process conduit 122 to the quencher 150. For example, the transfer conduit 140 can be configured to transfer heated ceramic powder, such as LRMO material powder, received from the outlet 124 to the quencher 150. The transfer conduit may be oriented substantially vertically (e.g., within a range of 30 degrees, 20 degrees, 10 degrees, 5 degrees, 2 degrees, 1 degree, or less from the vertical) so that the material (e.g., ceramic powder such as LRMO material powder) is transferred (e.g., falls) from the furnace outlet through the transfer conduit 140 to the quencher at least partially (or completely) by gravity.

[0060] In some embodiments, the system is configured to supply material (e.g., ceramic powder as LRMO material) to the quenching device at a relatively high temperature. For example, in some embodiments, the furnace and / or transfer conduit is configured to supply at least a portion (e.g., at least 50% by weight, at least 75% by weight, at least 90% by weight, at least 95% by weight, at least 99% by weight, or all) of the heated material (e.g., ceramic powder such as LRMO material powder) to the quenching device at a temperature within 10%, 5%, 2%, 1%, or less than the sintering temperature in the furnace (e.g., in the process conduit 122). For example, in Figure 1B, the transfer conduit 140 can be configured to limit the cooling of the incoming ceramic powder, such as LRMO material powder, and / or maintain its temperature.

[0061] In some embodiments, the furnace and / or transfer conduit is configured to supply at least a portion of the material (e.g., ceramic powder such as LRMO material powder) to the quenching device at a temperature of 800°C or higher, 850°C or higher, 875°C or higher, 900°C or higher, or higher. In some embodiments, the furnace and / or transfer conduit is configured to supply at least a portion of the material (e.g., ceramic powder such as LRMO material powder) to the quenching device at a temperature of 950°C or lower, 925°C or lower, 900°C or lower, or lower. Combinations of these ranges (e.g., 800°C to 950°C, 850°C to 925°C, 850°C to 900°C) are also possible.

[0062] For example, the transfer conduit 140 can be configured to supply ceramic powder, such as LRMO material powder, to the quenching device 150 at a quenching temperature of at least 800°C, such as 800°C to 950°C, or 850°C to 925°C, or 900°C. In some embodiments, the transfer conduit includes a heating element. For example, the transfer conduit 140 may include a heating element, such as a resistance heating element or a gas heating element, configured to heat the transfer conduit 140 so that the temperature at which the ceramic powder, such as LRMO material powder, is supplied to the quenching device 150 (quenching temperature) is maintained between the temperature at which it is supplied and the sintering temperature. In some embodiments, the transfer conduit 140 is covered at least partially (or entirely) with insulation to limit the cooling of the ceramic powder, such as LRMO material powder, so that it exits the transfer conduit 140 at the quenching temperature.

[0063] In some embodiments, the heat treatment system includes a quenching device. The quenching device can be configured to expose the material being quenched to a high-shear and / or turbulent environment. Such a high-shear and / or turbulent environment can retain at least some (or all) of the quenched material as loose powder. For example, a high-shear and / or turbulent environment can reduce or eliminate the aggregation of powder particles as the material is quenched, which may in some cases improve the quenching rate.

[0064] The quenching apparatus includes a container (e.g., a tank, a fluid circuit, a mass sedimentation device). The quenching apparatus can be configured to rapidly quench a heated material (e.g., heated ceramic powder such as sintered LRMO material powder) from a quenching temperature to a low temperature such as room temperature (e.g., 25°C). Figures 1A-1D show various embodiments of the quenching apparatus.

[0065] In some embodiments, the quenching apparatus is configured to quench at least a portion (e.g., at least 50% by weight, at least 75% by weight, at least 90% by weight, at least 95% by weight, at least 99% by weight, or all) of the heated material received (e.g., via a transfer conduit from a furnace) in 5 seconds or less, e.g., 1 second or less, 500 milliseconds or less, 400 milliseconds or less, or 300 milliseconds or less, or 200 milliseconds or less, 100 milliseconds or less, or faster. The quenching takes at least 100 milliseconds or more. For example, the quenching may occur from 100 milliseconds to 500 milliseconds, from 100 milliseconds to 400 milliseconds, or from 200 milliseconds to 300 milliseconds. Therefore, the quenching apparatus can be configured to quench at least a portion (e.g., at least 50% by weight, at least 75% by weight, at least 90% by weight, at least 95% by weight, at least 99% by weight, or all) of the heated material (e.g., heated ceramic powder such as sintered LRMO material powder particles) at an average rate of at least 50°C / sec, at least 87.5°C / sec, at least 100°C / sec, at least 200°C / sec, at least 500°C / sec, at least 1000°C / sec, at least 1750°C / sec, at least 2000°C / sec, at least 4375°C / sec, at least 5000°C / sec, or faster. In some embodiments, the quenching device is configured to quench at least a portion (or all) of the heated material (e.g., heated ceramic powder such as sintered LRMO material powder particles) at an average rate of 10,000°C / sec or less, 8,750°C / sec or less, 5,000°C / sec or less, 3,000°C / sec or less, or slower. Combinations of these ranges are possible (e.g., 50°C / sec to 10,000°C / sec, 87.5°C / sec to 8,750°C / sec, 1,750°C / sec to 8,750°C / sec, 4,375°C / sec to 8,750°C / sec).

[0066] In some embodiments, the quenching apparatus includes a batch device such as a stirred quenching vessel (e.g., a fluid tank) containing a quenching fluid such as water, alcohol, or oil, and optionally one or more additives as described above. For example, in Figure 1B, the quenching apparatus 150 includes a stirred quenching vessel 170 (e.g., a fluid tank). The vessel is configured to receive material (e.g., ceramic material such as LRMO sintered powder) output from a furnace (e.g., via a transfer conduit). The vessel 170 may include a mixing or stirring device (e.g., a rotary agitator (or stirrer)) 172 configured to mix the quenching fluid in the vessel 170 and / or normalize the temperature of the quenching fluid. The quenched material (e.g., ceramic powder such as LRMO material powder) may settle from the quenching fluid at the bottom of the vessel. In some embodiments, the quenching apparatus includes a plurality of vessels that are interchangeable when filling with quenching material (e.g., quenched ceramic powder such as LRMO material powder).

[0067] In some embodiments, the quenching system is configured to continuously circulate the quenched fluid. For example, Figure 1C is a schematic diagram of a continuous circulating quenching system 150, which in some embodiments may be included in the system 100 of Figure 1B. Referring to Figure 1C, the quenching system 150 is configured to circulate the quenched fluid and may include a quenching conduit 152, a return conduit 154, a pump 156, and a separation container 160. The pump 156 is configured to pump the quenched fluid through the conduits 152 and 154 to and from the separation container 160. The pump 156 includes any suitable fluid (e.g., liquid) pump. In particular, the pump 156 may be configured to generate a high-shear and / or high-turbulence fluid environment within the quenching conduit 152. In some embodiments, the pump 156 includes an in-line cooler configured to cool the quenched fluid. In some embodiments, the quenching system 150 includes a separate fluid cooler 158, such as a heat exchanger, configured to cool the quenched fluid. In some embodiments, the fluid cooler 158 is located on the return conduit 154. In some embodiments, the fluid cooler 158 includes a filter.

[0068] The quenching conduit 152 may be configured to receive heated material (e.g., heated ceramic powder, such as LRMO material powder, from the transfer conduit 140). The transfer conduit 140 may include a heater 151 and insulation. In some embodiments, the material (e.g., ceramic powder, such as LRMO material powder) may be transferred (e.g., dropped) from the transfer conduit into the quenching fluid in the quenching conduit, at least in part, by the force of gravity. The quenching device 150 may include a splash sleeve 153 to control the splashing of the quenching fluid as the material (e.g., ceramic powder, such as LRMO material powder) enters the quenching fluid. The splash sleeve 153 can form an airtight seal. In other words, the lower end of the transfer conduit 140, including the outlet opening, may be immersed in the quenching fluid in the quenching conduit 152. The splash sleeve 153 surrounds at least part (or all) of the lower end of the transfer conduit 140, protecting the lower end of the transfer conduit from the environment and providing an airtight seal to reduce or remove cold airflow from the outside to or from the lower end of the transfer conduit 140. The splash sleeve 153 may or may not be part of the insulation. The quenching device may be configured so that the heated material (e.g., heated ceramic powder such as LRMO material powder) is rapidly immersed in the quenching fluid after entering the quenching conduit.

[0069] High shear and / or turbulence in a rapidly cooled fluid can be configured to enhance the uniformity of the rapid cooling. For example, high shear or turbulence in a rapidly cooled fluid can be configured to enhance the uniformity of the rapid cooling rate of ceramic powders, such as LRMO material powders.

[0070] The separation vessel of the quenching device may be a vessel (e.g., a fluid tank) divided into a settling section and a return section. For example, referring again to Figure 1C, the separation vessel 160 may be a vessel (e.g., a fluid tank) divided into a settling section 162 and a return section 164 by a partition (e.g., a wall) 166 that extends from the top to the middle of the separation vessel 160 but does not extend to the bottom inner surface of the separation vessel 160. The quenched fluid and the quenched material (e.g., ceramic powder such as LRMO material powder) may be supplied to the top of the settling section by a quenching conduit. The material may be separated by gravity and settle from the quenched liquid and collect at the bottom of the separation vessel (e.g., below the partition plate 166).

[0071] In some embodiments, the system is configured to further dry the recovered powder (e.g., powder recovered from a sedimentation compartment). For example, the system may further include a desiccator. In some embodiments, the desiccator is configured to operate under reduced pressure relative to the ambient pressure. For example, the desiccator is a vacuum desiccator. In the context of this disclosure, it is understood that such additional drying (e.g., by a desiccator such as a vacuum desiccator) may facilitate improved powder drying, and as a result, the performance properties of the resulting material may be improved.

[0072] In the embodiment shown in Figure 1C, the quenched fluid then flows into the return compartment 164 and is supplied to the return conduit 154 by the pump 156. In some embodiments, the separation container 160 may include an optional filter 168 to prevent any unsettled material powder remaining in the quenched fluid (e.g., ceramic powder such as LRMO material powder) from entering the return conduit 154.

[0073] In some embodiments, the separation vessel consists of a centrifuge or is fluidly connected to a centrifuge. The centrifuge may be a batch centrifuge or a continuous centrifuge. For example, Figure 1D shows a schematic diagram of an embodiment in which the quenching device 150 consists of a separation vessel 160 comprising a centrifuge. In the embodiment shown in Figure 1D, the quenched liquid is led to a continuously rotating centrifuge. In some embodiments, the centrifuge uses a filter media of less than 10 microns, preferably 0.5 microns. The material is separated from the quenched liquid, discharged into a catch tank, and then recirculated and readjusted.

[0074] In some embodiments, heated powder particles are added directly to the separation container 160 (e.g., the inlet 155 is in direct fluid communication with the centrifuge). For example, as shown in Figure 1E, an exemplary quenching device 180 includes a splash sleeve 153 configured to receive powder particles (e.g., heated powder particles from the furnace outlet). In some embodiments, the inlet 155 is in direct fluid communication with the separation container 160 (e.g., so that powder particles enter the separation container 160 directly through the inlet 155). In some such embodiments, the quenching point occurs near the inlet 155 of the separation container 160. In some embodiments, the quenching device 180 is configured to circulate the quenching fluid and may include a quenching conduit 152, a return conduit 154, a pump 156, and / or the separation container 160. The pump 156 may be configured to pump the quenching fluid through the conduits 152 and 154 to and from the separation container 160. An optional filter 168 may be present (for example, within the conduit 154). In some embodiments, the quenching device 180 further includes a fluid cooler 158.

[0075] In some embodiments, for example, in the context of the embodiments shown in Figures 1B to 1E, the gravity-separated material / slurry can be recovered (for subsequent processing such as rinsing and / or drying) and removed from the quenching device. In some embodiments, the slurry pump is in fluid communication with the separation container 160 (for example, configured to facilitate the removal of the gravity-separated material / slurry). In some embodiments, the slurry (for example, containing quenched particles / powder) is a fluid slurry.

[0076] Advantageously, in some embodiments, a continuous circulating quenching fluid flow enables the scale-up of powder processing and allows continuous exposure of sintered material powders to a uniform quenching environment. Such a flow is particularly advantageous when an acid or other additive that modifies the surface of the powder particles is added to the aqueous quenching solution. Advantageously, the circulating quenching fluid flow allows for more uniform mixing of the additives in the water.

[0077] Although the system is described in part in the above disclosure in relation to the heat treatment of LRMO materials, the system is not so limited and can be used to heat treat any of the various materials (e.g., powder materials) such as ceramic powders that are transported through the system. For example, in various embodiments, the sintering temperature and / or quenching temperature of system 100 can be changed based on the sintering temperature of a particular sintering material. In particular, the sintering temperature may be higher or lower than the sintering temperature of the LRMO material. The quenching temperature of the sintering material in the transport conduit 140 can be adjusted accordingly. For example, transport conduit 140 may be configured to transport the sintering material to the quenching device 150 at a quenching temperature in the range of 0°C to 200°C lower than the sintering temperature, for example, a quenching temperature in the range of 0°C to 175°C lower than the sintering temperature, a quenching temperature in the range of 0°C to 150°C lower, a quenching temperature in the range of 0°C to 100°C lower, or a quenching temperature in the range of 0°C to 75°C lower.

[0078] In some embodiments, the heat treatment systems shown in Figures 1A to 1D include a furnace 110 configured to sinter a powder at a sintering temperature. The system may further include a quenching device 150 configured to quench at least a portion of the sintered powder in a quenching fluid. The system may further include a transfer conduit 140 configured to supply at least a portion of the sintered powder having a sintering temperature from the furnace 110 to the quenching device 150. The system may be configured to supply at least a portion of the sintered powder from the furnace 110 to the quenching device 150 in 500 milliseconds or less (e.g., 200 milliseconds or less, 100 milliseconds or less, and / or 50 milliseconds or less).

[0079] In some embodiments, the heat treatment system shown in Figure 1B includes an inclined rotary furnace 110 configured to sinter powder at a sintering temperature, a quenching device 150 configured to quench at least a portion of the sintered powder in a quenching fluid, and a transfer conduit 140 configured to supply at least a portion of the sintered powder having a sintering temperature from the inclined rotary furnace 110 to the quenching device 150 in 500 milliseconds or less.

[0080] In the embodiment shown in Figure 1B, the quenching device 150 is located below the inclined rotary furnace 110, and the transfer conduit 140 includes a substantially vertical tube connecting at least one outlet 124 of the inclined rotary furnace 110 to the inlet 155 of the quenching device 150. In some embodiments, the vertical tube is sealed. The transfer conduit 140 can be configured to supply at least a portion of the sintered powder from the inclined rotary furnace 110 to the quenching device 150 at least partially by gravity.

[0081] In some embodiments, the transfer conduit 140 is configured to supply at least a portion of the sintered powder having a sintering temperature from the furnace 110 to the quenching device 150 at a quenching temperature that is 0°C to 200°C lower than the sintering temperature. In some such embodiments, the quenching device is configured to quench the powder from the quenching temperature to a temperature in the range of 10°C to 15°C, 20°C to 20°C, and / or 120°C to 100°C, 80°C to 60°C to 50°C, 45°C to 40°C, 35°C to 30°C to 25°C, or lower. Other ranges are also possible. The system can be configured so that quenching occurs in 500 milliseconds or less (e.g., 200 milliseconds or less, and / or 100 milliseconds or less).

[0082] For example, in some embodiments, powder particles may be heated (e.g., to a sintering temperature in a furnace) and / or stirred (e.g., during heating) as described herein. In some embodiments, at least a portion of the particles having a heating temperature (e.g., sintering temperature) is transferred (e.g., at least partially) from the furnace through a transfer conduit (e.g., having an inlet) into a quenching fluid in a quenching apparatus described herein within 200 milliseconds or less (e.g., 100 milliseconds or less).

[0083] In some embodiments, the transfer conduit 140 is configured to supply at least a portion of a sintered powder having a sintering temperature from the inclined rotary furnace 110 to a quenching device 150 at a quenching temperature that is 0°C to 200°C lower than the sintering temperature, and the quenching device is configured to quench the powder from the quenching temperature to room temperature in 500 milliseconds or less. In some embodiments, the transfer conduit includes an insulating material (e.g., a sleeve 153 or additional insulating material) configured to limit the cooling of the powder, and a heater 151 configured to heat the transfer conduit 140 to at least the quenching temperature. The heater 151 can be embedded in the insulating material 153. In one embodiment, the sintering temperature is in the range of 800°C to 1000°C, the quenching temperature is at least 800°C, and the powder includes lithium-rich metal oxide (LRMO) material powder and / or S-LRMO. In one embodiment, the sintering temperature is in the range of 850°C to 1000°C, and the quenching temperature is at least 800°C; the powder comprises lithium-rich metal oxide (LRMO) material powder.

[0084] In some embodiments, at least a portion of the transfer conduit 140 extends into the quenching device 150, forming an airtight seal with the quenched fluid within the quenching device 150. For example, the lower end of the transfer conduit may extend into the quenched fluid located in the container 170 in Figure 1B, or into the quenched fluid flowing through the quenching conduit 152 in Figure 1C. In the embodiment of Figure 1B, the quenching device 150 includes a stirrer 172 and a container 170 configured to hold the quenched liquid. In the embodiment of Figure 1C, the quenching device 150 comprises (or includes) a continuous liquid loop quenching device. The continuous liquid loop quenching apparatus comprises: a quenching conduit 152 configured to receive at least a portion of the powder from a transfer conduit 140 and quench at least a portion of the powder in a quenching fluid; a separation container 160 configured to separate at least a portion of the quenched powder from the quenching fluid; a pump 156 configured to deliver the quenching fluid through the quenching conduit 152; and a return conduit 154 configured to supply the quenching fluid from the separation container 160 to the pump 156.

[0085] In some embodiments, the continuous liquid loop quenching apparatus 150 comprises: a quenching conduit 152 configured to receive at least a portion of the powder from a transfer conduit 140 and quench at least a portion of the powder in a quenching fluid; a separation container 160 comprising a batch or continuous centrifuge configured to receive at least a portion of the quenched powder and the quenching fluid; a pump 156 configured to pump the quenching fluid through the quenching conduit; and a return conduit 154 configured to supply the quenching fluid from a holding container of the centrifuge to the pump 156, wherein the centrifuge is configured to separate at least a portion of the quenched powder and send the quenching fluid to the holding container for collection, and the holding container is configured to pump at least a portion of the quenching fluid back to the quenching conduit.

[0086] In one embodiment shown in Figure 1B, the inclined rotary furnace 110 includes a process conduit 122 having an inlet 122A and an outlet 124, and a process conduit configured to transport powder through the rotary furnace 110; a drum 120 housing the process conduit 122 and configured to heat the process conduit 122 to a sintering temperature; a motor 138 configured to at least rotate the process conduit 122; and a base 130 supporting the drum 120 at a non-zero angle with respect to the horizontal, such that the inlet 122A of the process conduit 122 is higher than the outlet 124 of the process conduit 122, which is fluidly connected to the inlet of a transfer conduit 140. The outlet 124 of the process conduit 122 may include a plurality of openings arranged in an annular pattern around the sidewall of the process conduit 122 and extending through the sidewall of the drum 120 to the inlet of the transfer conduit 140.

[0087] Rapid breakdown of precursors LRMO materials can be formed from various precursor materials. For example, the precursor material may be a metal-organic compound containing a metal such as Li, Mn, and / or Ni, and a solubilizer such as an organic ligand. Examples of precursor materials include metal acetates, metal carbonates, metal nitrates, metal sulfates, and / or metal hydroxides.

[0088] In various embodiments, LRMO materials can be formed by thermally decomposing a precursor material, then sintering and quenching the resulting thermally decomposed LRMO material. The precursor material may include a gel formed via a sol-gel process. The gel may contain a non-fluid network of material (e.g., a colloidal network or polymer network) with a relatively low yield stress, whose entire volume expands due to a fluid (e.g., a liquid such as water). The gel may contain a network formed by covalent bonding or by other mechanisms such as physical aggregation. The sol-gel method involves converting monomers into a colloidal solution (sol), which serves as a precursor to the resulting gel (e.g., discontinuous particles or network polymer). The inventors have determined that rapidly decomposing the precursor gel may improve the homogeneity of the LRMO material. For example, in the sol portion of a sol-gel process, stoichiometric amounts of Li, Mn, and Ni-containing precursors can be mixed with water to form an aqueous mixture. For example, stoichiometric amounts of Li(CH3COO)*2H2O, Mn(CH3COO)2*4H2O, and Ni(NO3)2*6H2O can be mixed to form an aqueous mixture. However, this disclosure is not limited to specific precursors. For example, in some embodiments, all acetate precursors or all nitrate precursors (i.e., lithium nitrate, manganese nitrate, and nickel nitrate) can be used. In some embodiments, the mixture may contain a mole fraction excess of lithium acetate precursor of 0.01 to 0.20 to compensate for lithium loss during processing. Other ranges are also possible.

[0089] Subsequently, the mixture is heated to form a precursor gel. For example, the mixture can be heated at a temperature between 90°C and 150°C, for example, 100°C, for a sufficient time for gelation to occur. Other temperature ranges are also possible.

[0090] Next, the gel is thermally decomposed. For example, the gel can be heated to a temperature and time sufficient to extract (e.g., volatilize and / or decompose) the organic ligands and / or solubilizers such as solvents from the gel and to form a thermally decomposed LRMO material.

[0091] Pyrolysis can be carried out using conventional furnaces such as muffle furnaces and / or tubular furnaces. However, such devices generally have slow heating and cooling rates on the order of 1°C to 10°C per minute and do not employ any kind of direct radiant thermal energy input. Therefore, conventional furnaces may require at least 8 hours of processing time and a considerable amount of energy to form the pyrolyzed LRMO material.

[0092] According to various embodiments, rapid (e.g., high-speed) heating methods are used to form pyrolysis LRMO materials. For example, in one embodiment, microwave radiation can be used to heat-treat LRMO precursor materials (i.e., to rapidly decompose LRMO precursors such as gel precursors formed via sol-gel processing). For example, the microwave radiation may be direct microwave radiation. Other types of heating suitable for at least some embodiments include, but are not limited to, convection heating and / or radiant heating. Heating methods can also be used in combination. For example, pyrolysis may include convection heating, microwave radiation (e.g., direct microwave radiation), and / or radiant heating.

[0093] Microwaves are defined as electromagnetic waves with a wavelength of 1 mm to 1 m. Widely used household microwave ovens use microwave radiation at a frequency of approximately 2.45 GHz. Regulations limit the microwave frequencies that can be used in household and industrial applications. The mechanism of microwave heating is thought to be classified into two types: 1) heat is generated due to the ohmic effect caused by the flow of electric current under an external electric field generated by microwave radiation, and 2) heat is generated by friction as dipoles present in ceramics reorient under a changing electric field.

[0094] Microwave heating can enable lower heat treatment temperatures (e.g., thermal decomposition of precursors). Compared to conventional furnace heating processes, microwave heating can also shorten heating times due to very rapid localized heating. Furthermore, dense mixing of precursor materials can enable more efficient volumetric heating than conventional furnace heating processes.

[0095] In some embodiments, microwave heating is used to thermally decompose a precursor material to form a pyrolytic LRMO material. For example, the precursor material may contain ligands and / or metals that are highly susceptible to microwave radiation. Thus, in various embodiments, microwave radiation is utilized to heat the precursor and / or precursor gel to very high temperatures in a very short time. It has also been found that microwave heating provides very uniform thermal dispersion. Thus, although we do not wish to be constrained by theory, employing microwave radiation can favorably and dramatically alter the heating rate and the resulting microstructure and / or structure of the pyrolytic LRMO material. For example, microwave heating of a precursor gel can yield a very homogeneous pyrolytic LRMO material. The pyrolytic LRMO material may be in the form of inorganic ash that does not contain organic components (e.g., carbon-free or containing unavoidable amounts of carbon). Thus, microwave heating may make it possible to form a pyrolytic LRMO material without the need to omit calcination in a separate furnace.

[0096] For example, a precursor gel can be fed into a microwave furnace where microwave radiation is used to decompose the gel and form a pyrolytic LRMO material. For example, microwave radiation can be used to heat the gel to a temperature of at least 350°C, e.g., 350°C to 500°C, for a sufficient time to volatilize the ligands and / or solvents of the gel and form a pyrolytic LRMO material (e.g., LRMO inorganic ash). Other ranges are also possible. In various embodiments, the pyrolytic LRMO material can be formed in 30 minutes or less (e.g., 15 minutes to 30 minutes) using continuous microwaves or pulsed microwaves with a power level of less than 20,000 W per kg of microwave-heated material. Other ranges are also possible. Thus, microwave-based heat treatments can be configured to rapidly remove organic components from the precursor species (e.g., by evaporation and / or combustion) in order to form a pyrolytic LRMO material having improved structural properties such as a homogeneous cation and / or metal oxide distribution.

[0097] While the microwave thermal decomposition of precursor gels formed by the sol-gel method has been described above, in other embodiments, the precursors to be thermally decomposed by microwaves may be formed by other methods. For example, alternative precursor preparation methods include mechanical grinding / mixing, freeze-drying rotary evaporation, or coprecipitation. Another example of an alternative precursor preparation method is the use of a stationary convection oven. In one embodiment of the coprecipitation method, a coprecipitation precursor containing Mn and Ni hydroxides is mixed with lithium and / or other alkalis or alkaline carbonates and / or hydroxides. The resulting mixture can also be thoroughly mixed and heat-treated. In one embodiment of the coprecipitation method, a precursor containing Mn and Ni hydroxides can be mixed with lithium carbonate and coprecipitation can be performed. For example, solid precursors such as Li2CO3 or LiOH, nickel oxide, and manganese oxide can also be used. Such solid precursors may also have an excess of Li-containing precursor (e.g., lithium carbonate or lithium hydroxide) in a mole fraction excess of 0.01 to 0.20 to overcome the loss of lithium content during processing. The precursors prepared by any of these methods can also be subjected to microwave pyrolysis to form pyrolytic LRMO materials (i.e., LRMO inorganic ash). As will be described in more detail below, the methods, conditions, parameters, and / or processing steps described above can be applied in some embodiments to the substituted LRMO materials described herein.

[0098] The pyrolysis LRMO material (i.e., LRMO inorganic ash) can then be mixed and pulverized (e.g., milled) to form a precursor LRMO powder. Next, the precursor LRMO powder can be heat-treated (e.g., sintered) in any suitable heat treatment apparatus, such as in a tubular furnace or muffle box, to form a sintered LRMO material. For example, the precursor LRMO powder material can be heated (e.g., sintered) at a heat treatment temperature (e.g., at least 800°C, e.g., 900°C) for 12 to 24 hours, and then the sintered LRMO material can be rapidly or ultra-rapidly quenched as described above to form a quenched LRMO material. The quenched LRMO material can then be dried and optionally refractored (e.g., milled) to form an LRMO active material (e.g., cathode active material powder). This LRMO cathode active material powder can be mixed with a binder or other inert cathode material to form the cathode of a lithium-ion battery.

[0099] According to various embodiments, methods for forming LRMO materials may include a combination of rapid heating, such as microwave heating, and rapid or ultra-rapid cooling in at least part of the heat treatment to produce LRMO materials with unexpectedly high performance. Specifically, this process can advantageously produce LRMO materials with a high degree of atomic / cation disorder / uniformity (quantifiable using X-ray diffraction), and LRMO materials that are free from or substantially free of surface segregation of nickel or nickel oxide in particles (e.g., crystallites) observable by transmission electron microscopy. Combining these material properties yields cathode active materials that exhibit little to no capacity degradation over 100 to 1000 charge-discharge cycles, substantially reduced or eliminated average discharge voltage drop during cycles, and rate performance suitable for commercial use.

[0100] According to various embodiments, methods of embodiments including microwave heating and / or rapid / ultrarapid quenching steps can be used to form LRMO active materials that are not plagued by the chemical instability of LRMO materials prepared by different methods. In particular, the quenching or ultrarapid quenching steps can be used to form LRMO active materials with reduced Ni surface segregation and improved structural homogeneity compared to conventional LRMO materials that are slowly cooled after sintering. In various embodiments, the microwave heating treatment described above can be used in combination with rapid or ultrarapid quenching to form LRMO active materials. For example, a pyrolysis LRMO material formed using microwave decomposition may be subjected to rapid or ultrarapid quenching after sintering. As will be described in more detail below, the methods, conditions, parameters, and / or processing steps described above can be applied to the substituted LRMO materials described herein in some embodiments.

[0101] In one embodiment, the cathode electrode (i.e., positive electrode) comprises an LRMO active material comprising powder embedded in a binder. The powder may have an average particle / aggregate size of 0.1 μm to 10 μm and an average crystal (i.e., crystallite) size of 25 nm to 500 nm. The powder (for example, embedded in the binder) may include particles having an average maximum cross-sectional size of 0.1 microns or more, 0.2 microns or more, 0.5 microns or more, or 1 micron or more. The powder (for example, embedded in the binder) may include particles having an average maximum cross-sectional size of 10 microns or less, 5 microns or less, 2 microns or less, or less. Combinations of these ranges (e.g., 0.1 microns to 10 microns) are also possible. Other ranges are also possible. The powder may have crystals (e.g., crystallites) having an average maximum cross-sectional size of 25 nm or more, 50 nm or more, 100 nm or more, 150 nm or more, or larger. The powder may have crystals (e.g., crystallites) having an average maximum cross-sectional dimension of 500 nm or less, 300 nm or less, 200 nm or less, or smaller. Combinations of these ranges (e.g., 25 nm to 500 nm) are also possible. Other ranges are also possible. In one embodiment, the particles of the LRMO active material powder may have at least one of the following: a spinel surface layer (e.g., due to a carbohydrate additive in the quenching bath), a carbon coating, and / or passivated oxygen bonds on the surface (e.g., due to an acid additive in the quenching bath). The cathode electrode may be included in a battery such as a lithium-ion battery, which also includes an anode electrode (i.e., negative electrode), an electrolyte, and a separator.

[0102] In one embodiment, the cathode electrode active material is of the chemical formula Li x (Mn y Ni 1-y ) 2-xRepresented by O2 (wherein x is greater than 1.05 and less than 1.25, and y is between 0.1 and 0.95). The active material may contain a layered hexagonal (e.g., rhombohedral) phase and a monoclinic phase, at least before the battery, including the cathode electrode, is first electrochemically cycled. The active material has (i) an X-ray diffraction peak intensity ratio of 0.32 or greater, e.g., between 0.33 and 0.346; and / or (ii) an X-ray diffraction peak intensity ratio of (003) to (104) of 2 or greater, e.g., between 2.01 and 2.575; and / or (iii) if the cathode electrode is included in a lithium-ion battery, a specific capacity at the first discharge (e.g., at a C / 2 rate) of at least 200 mAh / g, e.g., at least 200 mAh / g and 230 mAh / g; and / or (iv) if the cathode electrode is included in the lithium-ion battery, the lithium-ion battery may exhibit at least one of the following after 100 charge-discharge cycles: a mean discharge voltage loss of less than 10% at a C / 20 rate; and / or (v) if included in the cathode of the lithium-ion battery, at least one of the following can be observed over at least 100 charge-discharge cycles (e.g., over 200 charge-discharge cycles at C / 5): a capacity decrease of less than 10%, e.g., less than 5% (e.g., a capacity decrease or increase of 0 to 4%). In one embodiment, the lithium-ion battery may include lithium or graphite as the negative electrode.

[0103] In one embodiment, the average discharge voltage of a battery (e.g., a lithium-ion battery) does not decrease by more than 5% (e.g., between 0% and 4%) over 50 C / 20 (charge)-C / 2 (discharge) charge-discharge cycles; and / or, the discharge capacity of the battery exceeds 80% of its original capacity after 800 C / 20-C / 2 charge-discharge cycles.

[0104] Replacement LRMO material In one abstract, a substituted lithium-rich metal oxide (S-LRMO) material is provided in which at least a portion of the lithium is substituted with sodium, potassium, calcium, and / or magnesium. According to various embodiments, the cathode active material comprises a substituted lithium-rich metal oxide (S-LRMO) material in which at least a portion of the lithium is substituted with sodium, potassium, calcium, and / or magnesium. In this specification, S-LRMO materials may also be called substituted alkali / alkali-atom-rich metal oxide (ARMO) materials. The general formula for S-LRMO materials is: Li[Li x A y M z ]O b It can be expressed as follows: In the formula, A is at least one alkaline earth element and / or an alkali element other than lithium, (x+y) is greater than 0 and less than 0.3, y > 0.05, z = 1 - (x+y), M includes manganese (Mn) and nickel (Ni), and b is between 1.8 and 2.2 depending on the net oxidation state of M.

[0105] In some embodiments, A is an alkaline earth element such as beryllium, magnesium, calcium, strontium, barium, and radium. In some embodiments, A is an alkali element other than lithium, such as sodium, potassium, rubidium, cesium, and francium. In an exemplary series of embodiments, A is selected from the group consisting of Na, K, Ca, and / or Mg.

[0106] In some embodiments, the S-LRMO material is given by the general formula: Li[Li x A y M z ]O b It can be expressed as follows. In the formula, A is at least one alkaline earth element and / or an alkali element other than lithium, such as Na, K, Ca, and / or Mg; (x+y) is between 0 and 0.3, y > 0.05, z = 1 - (x+y); M is a combination of transition metals, including at least manganese (Mn) and nickel (Ni); and b is between 1.8 and 2.2 depending on the net oxidation state of M. Preferably, b = 2. In one embodiment, (x+y) is greater than 0.1 and less than 0.25, for example 0.2, and y is between 0.05 and 0.15, for example 0.06 and 0.14. In one embodiment, the material exhibits the crystallinity and phase content commonly seen in lithium-rich layered metal oxides (i.e., embodiments of unsubstituted LRMO materials), with no evidence of other crystalline phases. In one embodiment, the S-LRMO material in its original state (e.g., before initial charging) may have distinct hexagonal (e.g., rhombohedral) and monoclinic phases. In some embodiments, the two phases may be arranged in a layered structure. Those skilled in the art will understand, based on the teachings herein, that the stoichiometry "O2" in the chemical formulas of LRMO and / or S-LRMO is not intended to be strictly stoichiometric, and that the actual elemental amount of oxygen may vary slightly to accommodate slight variations in the average transition metal oxidation states of other components of the material (e.g., the oxidation states of the transition metals) (e.g., the number of moles of oxygen per unit molar of active material is between 1.9 and 2.1). For example, M may contain 50-80 atomic% Mn, 20-50 atomic% Ni, and 0-10 atomic% of other elements, including, for example, Ti, Al, Fe, Co, or any combination thereof. In various embodiments, up to 20% of the total Li content in the material may be replaced by one or more alkali elements and / or one or more alkaline earth elements other than Li. For example, 0.5% or more, 1% or more, 2% or more, 5% or more, 10% or more, or more of Li can be replaced by at least one of Na, K, Mg, and Ca. In some embodiments, up to 13%, up to 15%, up to 20%, or more of Li can be replaced by at least one of Na, K, Mg, and Ca.For example, Li in amounts between 0.5% and 20%, for instance between 1% and 15%, or between 2% and 13%, can be substituted with at least one of Na, K, Mg, and Ca. Therefore, the atomic ratio of A to lithium in the above formula can be between 0.5:95.5 and 20:80. In other words, the ratio of A to (1+x) in the above formula can be between 0.5:95.5 and 20. Other ranges are also possible. When heat-treated as described above (sintering, rapid cooling, etc.), S-LRMO exhibits a classical lithium-rich crystal structure that combines some of the characteristics of trigonal (R-3m) and monoclinic (C2 / m) crystal structures, and no obvious secondary phases are observed. In other words, S-LRMO contains both hexagonal and monoclinic phases, and the trigonal crystal system is a type of hexagonal crystal system (i.e., a genus).

[0107] In some embodiments, 0.5% or more, 1% or more, 2% or more, 5% or more, 10% or more, or more of Li is substituted with Na. In some embodiments, up to 13%, up to 15%, up to 20%, or more of Li is substituted with Na. For example, 0.5% to 20%, for example, 1% to 15%, or 2% to 13% of Li can be substituted with Na. Other ranges are also possible.

[0108] In some embodiments, 0.5% or more, 1% or more, 2% or more, 5% or more, 10% or more, or more of Li is substituted with K. In some embodiments, up to 13%, up to 15%, up to 20%, or more of Li is substituted with K. For example, 0.5% to 20%, for example, 1% to 15%, or 2% to 13% of Li can be substituted with K. Other ranges are also possible.

[0109] In some embodiments, 0.5% or more, 1% or more, 2% or more, 5% or more, 10% or more, or more of Li is substituted with Mg. In some embodiments, up to 13%, up to 15%, up to 20%, or more of Li is substituted with Mg. For example, 0.5% to 20%, for example, 1% to 15%, or 2% to 13% of Li can be substituted with Mg. Other ranges are also possible.

[0110] In some embodiments, 0.5% or more, 1% or more, 2% or more, 5% or more, 10% or more, or more of Li is substituted with Ca. In some embodiments, up to 13%, up to 15%, up to 20%, or more of Li is substituted with Ca. For example, 0.5% to 20%, for example, 1% to 15%, or 2% to 13% of Li can be substituted with Ca. Other ranges are also possible.

[0111] In some embodiments, the S-LRMO material (for example, as a cathode active material) is of the formula Li[Li e A f M g ]O h It can be expressed as follows (where e is 0.06 or less, f is 0.14 or more, g = 1 - (e + f), A contains at least one of Na, K, Ca, and Mg, M contains Mn and Ni, and h is between 1.8 and 2.2). Other ranges are also possible.

[0112] In some embodiments, cobalt is not present in the S-LRMO material, or is present in relatively small amounts. For example, in some embodiments, the atomic percentage of cobalt in the S-LRMO is zero, or less than or equal to 10 atomic%, 5 atomic%, 2 atomic%, 1 atomic%, 0.5 atomic%, 0.2 atomic%, 0.1 atomic%, 0.05 atomic%, 0.02 atomic%, 0.01 atomic%, 0.005 atomic%, 0.002 atomic%, 0.001 atomic%, or less. Other ranges are also possible.

[0113] In some embodiments, S-LRMO (for example, as a cathode active material) is of the formula Li 1.14 Na 0.06 Mn 0.6 Ni 0.2 It is represented by O2. In some embodiments, S-LRMO (for example, as a cathode active material) is represented by the formula Li 1.06 Na 0.14 Mn 0.6 Ni 0.2 It is represented by O. In some embodiments, S-LRMO (for example, as a cathode active material) is represented by the formula Li 1.015Na 0.155 Mn 0.58 Ni 0.25 It is represented by O2. In some embodiments, S-LRMO (for example, as a cathode active material) is represented by the formula Li 1.013 Na 0.157 Mn 0.52 Ni 0.32 It is represented by O2. In some embodiments, S-LRMO (for example, as a cathode active material) is represented by the formula Li 1.06 K 0.14 Mn 0.6 Ni 0.2 It is represented by O2. S-LRMO materials can be formed using methods similar to those described above for LRMO materials. For example, S-LRMO materials can be produced using precursor materials formed by sol-gel methods, solid-state methods, or coprecipitation methods. Precursor materials may include metal-organic precursors of Li, Na, K, Ca, Mg, and 1 or more transition metals and / or Al. For example, metal-organic precursors can be selected from acetates, carbonates, nitrates, sulfates, and / or hydroxides of Li, Na, K, Ca, Mg, Mn, Ni, and optionally Fe, Co, Al, and / or Ti. In some embodiments, the precursor contains a mole fraction excess of lithium, sodium, and / or potassium metal-organic precursors of 0.01 to 0.20. In some embodiments, the precursor may include a mole fraction excess of lithium and / or sodium metal-organic precursors of 0.01 to 0.20. For example, the sol-gel may include a mole fraction excess of lithium and / or sodium metal-organic precursors of 0.01 to 0.20. In some embodiments, the precursor comprises a lithium and / or sodium metal hydroxide precursor with a mole fraction excess of 0.01 to 0.20. For example, the sol-gel may include a lithium and / or sodium metal hydroxide precursor with a mole fraction excess of 0.01 to 0.20. Other ranges are also possible. The precursor can be mixed (e.g., with a solution containing water) to form a mixture. The mixture of precursors can also be heated to form a gel.

[0114] The precursor may be thermally decomposed (e.g., to form an LRMO material) (for example, as a mixture such as a gel). The precursor can be thermally decomposed to form an S-LRMO material by firing at a temperature of 250°C to 600°C, for example, 300°C to 500°C, for a period of 2 to 8 hours, for example, 4 to 6 hours. In some embodiments, the precursor can be thermally decomposed using microwave heating as described above. The decomposed precursor material is then sintered at a sintering temperature (e.g., to form a sintered S-LRMO material). The decomposed precursor material can then be fired at a temperature of at least 800°C, for example, 850°C to 1000°C, for example, 900°C to 950°C, for a period of 8 to 14 hours, for example, 9 to 12 hours, or 10 to 11 hours to form an S-LRMO material. Other ranges are also possible.

[0115] In some embodiments, the S-LRMO material is sintered at a sintering temperature. The sintering temperature may refer to the temperature of the environment in which the S-LRMO is present during sintering (e.g., the furnace temperature). In some embodiments, the sintering temperature is at least 800°C, at least 825°C, at least 850°C, at least 875°C, at least 900°C, or higher. In some embodiments, the sintering temperature is 1000°C or less, 950°C or less, 925°C or less, or lower. Combinations of these values ​​(e.g., at least 800°C and 1000°C or less, at least 850°C and 950°C or less, at least 900°C and 950°C or less) are also possible. Other ranges are also possible.

[0116] The S-LRMO material can be ultra-rapidly cooled from a quenching temperature to room temperature in a quenching fluid or bath as described above to form the S-LRMO active material. For example, the S-LRMO material may be quenched from a sintering temperature of at least 800°C, e.g., 800°C to 1000°C, or 850°C to 950°C to room temperature (e.g., 25°C) for a time of 500 milliseconds or less, or 200 milliseconds or less, e.g., 100 milliseconds to 500 milliseconds, or 200 milliseconds to 100 milliseconds. Other ranges are also possible. In some embodiments, the quenching temperature and the sintering temperature are the same or substantially the same.

[0117] In some embodiments, the quenching temperature is 800°C or less, 700°C or less, 600°C or less, 500°C or less, 400°C or less, 300°C or less, 200°C or less, or 100°C or less. In some embodiments, the quenching temperature is 50°C or more, 100°C or more, 200°C or more, 300°C or more, 400°C or more, 500°C or more, 600°C or more, 700°C or more, or 800°C or more. Combinations of the above reference ranges (e.g., 800°C or less and 100°C or more) are also possible. Other ranges are also possible.

[0118] Excess alkali metals and / or alkaline earth metals, as well as Ni and Mn atoms, can be homogeneously and uniformly distributed throughout the transition metal crystal lattice sites in the S-LRMO material. This ensures that there are no crystal volumes larger than 3 × 3 × 3 nm in the material where the ratio of Ni, Mn, A (where A is at least one of Na, K, Ca, and Mg), and Li atoms differs from the average ratio of Ni, Mn, Na, K, Ca, Mg, and Li atoms in the bulk material by more than 3%.

[0119] According to various embodiments, S-LRMO materials reduce the amount of Li used by substituting Li with a less expensive element. This results in S-LRMO materials offering reduced material costs compared to unsubstituted LRMO materials. Furthermore, S-LRMO materials also offer unexpected capacity stability, rate capability, and unexpectedly high voltage compared to conventional unsubstituted LRMO materials. Moreover, in the context of this disclosure, it has been unexpectedly observed that relatively high amounts of lithium in LRMO materials can be substituted with different cations (e.g., alkali and / or alkaline earth metals such as sodium, potassium, magnesium, and / or calcium) to form S-LRMOs while maintaining substantially the same crystal structure and properties as the unsubstituted analogs. For example, it was surprising that relatively high levels of lithium substitution (e.g., over 5% and up to 20%) could be obtained without observing substantial occurrence of potentially harmful phenomena such as the formation of secondary crystalline phases. This is because in lithium metal oxide electrode active materials containing nickel and manganese, substituting some of the Li results in the formation of secondary crystalline phases (Na 0.7 This is in contrast to predictions from literature that reported the observation of MnO2 (Du, K., et al. Li[Li for lithium-ion batteries]). 0.2 Mn 0.54 Ni 0.13 Co 0.13 Sodium additives that improve the rate performance of O2 materials (Journal of Power Sources, 244, 29-34). Substantial generation of such secondary phases has not been observed in the materials of this disclosure. While we do not wish to be bound by any particular theory, it is thought that the use of the techniques of this disclosure (e.g., using rapid quenching in water) may be one reason why the high degree of lithium substitution was observed without impairing the desired crystalline and / or electrochemical properties.

[0120] In one embodiment, a method for forming an active material for the positive electrode of a lithium-ion battery includes quenching the active material powder in water. In one embodiment, the method further includes calcining the active material powder before quenching. The active material can be calcined at a temperature of at least 800°C. The water before quenching may be at room temperature, and the active material powder can be quenched at a rate of at least 1750°C / second.

[0121] In one embodiment, the active material comprises a layered substituted lithium-rich nickel-manganese oxide. Excess Li, Ni, and Mn atoms can be homogeneously and uniformly distributed throughout the transition metal crystal lattice sites, so that there are no crystal volumes exceeding 3 × 3 × 3 nm that show a difference of more than 3% between the ratio of Ni, Mn, and Li atoms in the material and the average ratio of Ni, Mn, and Li atoms in the bulk material. The active material powder particles may be in the form of aggregates having an average size in the range of 0.1 μm to 20 μm, and the aggregates of the active material powder consist of crystallites having an average size in the range of 25 nm to 500 nm. After quenching, the active material powder may contain a composite of hexagonal and monoclinic phases, a combination of the R-3m phase of LiAMO2 and the C2 / m phase of (LiA)2MnO3, where M is at least one of Ni or Mn, and A is a combination of a non-lithium alkali element and an alkaline earth element. The active material powder may contain a solid solution having a crystalline structure that mainly or completely exhibits C2 / m symmetry. The active material powder may contain a solid solution having a crystalline structure that mainly or completely exhibits R-3m symmetry.

[0122] In one embodiment, the quenched water contains an additive dissolved therein. The water may contain between 0.01 moles and 1.0 mole of the additive per liter. In one embodiment, the additive comprises an acid, which can be selected from sulfuric acid, citric acid, acetic acid, phosphoric acid, hydrochloric acid, ammonium phosphate, or a combination thereof. In another embodiment, the additive comprises a carbohydrate, which can be selected from fructose, galactose glucose, lactose, maltose, sucrose, or a combination thereof.

[0123] In one embodiment, the active material is placed at the positive electrode of a lithium-ion battery cell, which further includes a negative electrode and an electrolyte. In this context, the positive electrode corresponds to the cathode and the negative electrode corresponds to the anode. The active material contains a hexagonal phase and a monoclinic phase before the electrochemical cycle of the battery, and the active material powder does not contain the monoclinic phase after the electrochemical cycle.

[0124] In one embodiment, the positive electrode material in the battery cell has a specific capacity of at least 230 mAh / g (at a charging rate of C / 20) after undergoing 50 electrochemical cycles at a discharge rate of up to C / 2.

[0125] In one embodiment, a lithium-ion battery cell comprises a negative electrode; an electrolyte; and a positive electrode containing a layered lithium-rich nickel-manganese oxide active material, the battery cell having a specific capacity of at least 215 mAh / g (at a rate of C / 20) after 50 electrochemical cycles at discharge rates up to C / 2.

[0126] In one embodiment, the active material powder particles are in the form of aggregates having an average size of 0.1 μm to 10 μm, and the active material powder aggregates are composed of crystallites having an average crystal size of 25 nm to 500 nm. The active material powder particles may have at least one of a spinel surface layer, a carbon coating, or passivation oxygen bonds on their surface.

[0127] In some embodiments, the ratios of Ni, Mn, and alkali and / or alkaline earth metal atoms in less than 10% (e.g., less than 5%, less than 2%, less than 1%, less than 0.1%, or less) of the non-overlapping crystal volume greater than 3 × 3 × 3 nm in the material differ by more than 3% compared to the average ratio of Ni, Mn, Li, and alkali and / or alkaline earth metal atoms in the bulk material. Such spatial distributions may be due to a high degree of cation disorder (e.g., due to a homogeneous distribution of Li, K, Na, Ca, Mg, Ni, and / or Mn atoms). Other ranges are also possible.

[0128] In some embodiments, in materials where the ratio of Ni, Mn, and alkali metal atoms and / or alkaline earth metal atoms differs by more than 3% compared to the average ratio of Ni, Mn, Li, and alkali metal atoms and / or alkaline earth metal atoms in the bulk material, there are no crystal volumes exceeding 3 × 3 × 3 nm. Such spatial distribution may be due to a high degree of cation disorder (e.g., due to a homogeneous distribution of Li, K, Na, Ca, Mg, Ni, and / or Mn atoms).

[0129] In one embodiment, the excess Li, K, Na, Ca, Mg, Ni, and / or Mn atoms are homogeneously and uniformly distributed throughout the transition metal crystal lattice sites, so that there are no crystal volumes exceeding 3 × 3 × 3 nm in the material where the difference between the ratio of Ni, Mn, and alkali metal atoms and / or alkaline earth metal atoms exceeds 3% compared to the average ratio of Ni, Mn, and Li atoms in the bulk material.

[0130] Examples The following examples illustrate specific embodiments of the present invention, but do not represent the entire scope of the invention.

[0131] Example 1 Formula Li x (Mn y Ni 1-yLRMO powder having )2-xO2 (where x=1.16 and y=0.7) was prepared by the following method. In particular, a precursor gel was prepared using a sol-gel solid synthesis method. The synthesis of the sol involved the formation of an aqueous mixture containing stoichiometric amounts of Li(CH3COO)*2H2O, Mn(CH3COO)2*4H2O, and Ni(NO3)2*6H2O. The mixture was heated at 100°C until a gel was formed. This gel was poured into an alumina crucible and calcined at 400°C for 90 minutes to obtain organic matter-free ash. The obtained ash was pulverized, recalcined in the crucible at 500°C for 3 hours, allowed to cool naturally, and then pulverized again. The powder was then calcined at 900°C for 24 hours and rapidly cooled. All sintering was carried out in a box furnace under atmospheric pressure with a fume (or smoke, steam, gas; fume) hood. All rapid cooling was performed after heating at 900°C for 12 to 24 hours.

[0132] Figure 2A is a photograph of a rapid quenching system 200 according to an alternative embodiment of the present disclosure. Figure 2B includes four consecutive video capture time-lapse images taken at 30 frames per second, illustrating the rapid quenching process according to various embodiments of the present disclosure.

[0133] Referring to Figures 2A and 2B, the LRMO material was placed in a tubular furnace 210 and heated to 900°C. The heated LRMO material was discharged from the tubular furnace 210 and rapidly cooled to room temperature in a rapid cooling bath 250. The tubular furnace 220 rotates during operation so that its contents can be poured instantaneously into the rapid cooling bath 250. The time from when the LRMO material leaves the 900°C furnace 210 until it is rapidly cooled to room temperature is less than 500 milliseconds, for example less than 200 milliseconds, thereby forming the LRMO active material. After rapid cooling, the LRMO material was filtered from the water in the rapid cooling bath 250 and dried in a vacuum oven.

[0134] In the first comparative example, the LRMO material was slowly cooled in the furnace after sintering at 900°C. In the second comparative example, the sintered LRMO material was dumped onto a metal plate and cooled. In the third comparative example, the LRMO material was first slowly cooled to room temperature, then inserted into a tubular furnace 210 for a rapid cooling process, and held at 900°C for 30 to 120 minutes before the rapid cooling process.

[0135] In another example, LRMO powder was formed using a rapid precursor decomposition process. Specifically, the sol-gel precursor material described above was decomposed with microwaves to form LRMO powder with an improved component distribution. In particular, when irradiated with microwaves, the organic components absorbed the microwave energy, causing the organic components of the precursor material to rapidly volatilize. In this way, the thermal energy generated by microwave radiation uniformly mixed the LRMO components at the molecular level. The obtained LRMO powder was sintered at 900°C for 12 to 24 hours, and then rapidly cooled as described above.

[0136] Multiple large batches (up to 1 kg) of cathode material were manufactured, with or without microwave decomposition and ultra-rapid quenching.

[0137] Material property evaluation According to various embodiments of this disclosure, Figures 3 and 4 show Li x (Mn y Ni 1-y ) 2-x This is a graph of the X-ray diffraction (XRD) patterns of the O2 material (where x=1.2 and y=0.75 in the equation). The XRD pattern in Figure 3 was generated from layered LRMO active material that was not rapidly cooled by immersion in water, while the XRD pattern in Figure 4 was generated from layered LRMO active material that was rapidly cooled by immersion in water.

[0138] XRD pattern evaluation revealed that the LRMO material possesses both a hexagonal (e.g., rhombohedral) phase related to LiNiO2 with space group (R-3m) and a monoclinic phase related to Li2NiO3 with space group (C2 / c).

[0139] Figure 5 shows Li x(Mn y Ni 1-y ) 2-x The graph shows the X-ray diffraction results of the O2 material (wherein x=1.16 and y=0.7), which was treated with microwave heating for 5 minutes prior to the high-temperature firing step according to various embodiments of the present disclosure. Referring to Figure 5, it is of interest that this microwave-resolved material has an X-ray diffraction pattern that matches that of a highly crystallized and optimized material, which includes the rhombohedral phase LiNiO2-related space group (R-3m) and the monoclinic phase Li2NiO3-related space group (C2 / c). Therefore, the material is suitable for LRMO formation using annealing at 900°C and rapid and / or ultra-rapid quenching as described above.

[0140] Figure 6 shows Li x (Mn y Ni 1-y ) 2-x This graph shows the X-ray diffraction results of an O2 material (where x=1.16 and y=0.7 in the equation), which was processed using microwave heating and ultra-rapid quenching according to various embodiments of this disclosure. Referring to Figure 6, all expected peaks are present and clearly visible.

[0141] Figure 7A is an example of a tunneling electron microscope (TEM) high-angle annular dark-field imaging (HAADF) atomic map micrograph of a typical LRMO material that was not rapidly cooled before electrochemical cycling, as published in the literature (H. Zheng et al., "Recent Progress and Challenges of Lithium-Rich Manganese Cathode Materials for High-Energy Lithium-Ion Batteries," Materials Energy Today, Volume 18, December 2020, P100518). As can be seen from the micrograph in Figure 7A, the initial LRMO material showed significant segregation of nickel and manganese within the particles.

[0142] Figure 7B shows TEM HAADF atomic map micrographs of LRMO materials produced by rapid quenching before electrochemical cycling, according to various embodiments of the present disclosure. As can be seen from the micrographs in Figure 7B, the LRMO materials did not exhibit significant nickel / manganese segregation within the particles. Therefore, rapid or ultra-rapid quenching reduces or eliminates nickel segregation on the particle surface and uniformly mixes nickel and manganese in the bulk of the LRMO material.

[0143] Crystalline uniformity, cation disorder, surface passivation One method for evaluating the degree of disorder among metal cations in a material is to use the ratio of peak intensities in the X-ray diffraction pattern. Specifically, the ratio of the intensity of the (003) peak to the (104) peak is generally known as a rough measure of the electrochemical activity of mixed cation materials with a predominantly layered crystalline structure, while the ratio of the sum of the intensities of the (006) and (102) peaks to the intensity of the (101) peak is a measure of cation disorder. Based on this, materials that have been microwave-treated in a decomposition process and then rapidly cooled exhibit significantly higher electrochemical activity and a lower degree of cation order (and therefore higher degree of cation disorder) than materials that have been slowly cooled.

[0144] [Table 2] JPEG2026513621000003.jpg47168

[0145] Table 2 shows the XRD peak intensity ratio of a comparative example LRMO material (first row) that underwent slow rapid cooling after sintering, and an exemplary LRMO material (second row) that underwent ultra-rapid rapid cooling after sintering. Both materials also contain Li. x (Mn y Ni 1-y ) 2-xIt contains O2 (wherein x=1.2 and y=0.75). Importantly, the exemplary ultra-rapidly cooled material exhibits significantly higher electrochemical activity than the comparative material and XRD properties indicating increased atomic disorder in a material with higher cation disorder / metal oxide homogeneity. Specifically, the exemplary material shows an increased ratio of the sum of the intensities of the (006) and (102) peaks to the intensity of the (101) peak, which was 9% in this case. This significant increase in cation disorder indicates a situation where Ni and Mn atoms are more completely mixed (and thus not grouped) in the material. For this reason, such exemplary materials are sometimes called "cationically disordered lithium-rich lithium manganese nickel oxide," and these data demonstrate that different material states can be created depending on the processing conditions used, particularly the cooling rate used.

[0146] Figures 11-14 are charts showing the X-ray diffraction pattern results of S-LRMO materials containing various amounts of Na and / or K as described in the preceding section, according to various embodiments of the present disclosure. The S-LRMO materials were prepared using the heat treatment and ultra-rapid cooling treatment described above. As shown in Figures 11-14, the S-LRMO materials had the classic phase purity of LRMO materials. The XRD data are also consistent with materials showing a high degree of cation mixing / disorder at transition sites in the material.

[0147] Figures 15 to 22 are graphs showing the electrochemical performance of lithium-ion cells formed using various identified S-LRMO materials. In particular, Figures 15 and 16 are graphs of voltage-to-reverse capacitance for the first two cycles and cycles 13 to 26, respectively, of cells containing S-LRMO material, where the formula for the S-LRMO material is Li[Li 0.14 Na 0.06 Mn 0.6 Ni 0.2 ]O2. Figure 17 is a graph of discharge ratio capacity versus cycle number (i.e., cycle stability), and the inset is a graph of voltage versus ratio capacity of a cell containing S-LRMO material, in which case the formula for S-LRMO material is Li[Li 0.14 Na 0.06Mn 0.6 Ni 0.2 O₂. Figure 18 is a plot of the charge-discharge specific capacity (i.e., voltage vs. specific capacity) of a cell containing the S-LRMO material, in which 12.5% of Na is substituted for lithium. Figure 19 is a plot of the cycle number vs. charge-discharge efficiency and discharge specific capacity of a cell containing the S-LRMO active material. Figure 20 includes a graph of discharge specific capacity vs. cycle number (i.e., cycle stability) on the left side and a graph of voltage vs. specific capacity of a cell containing the S-LRMO material on the right side. The S-LRMO material formulas in Figures 18-20 are Li[Li 0.06 Na 0.14 Mn 0.6 Ni 0.2 O₂. Looking at Figures 21 and 22, they are graphs of voltage vs. specific capacity for the first 2 cycles of a cell containing the S-LRMO material, and the formulas of the S-LRMO materials are Li[Li 0.06 K 0.14 Mn 0.6 Ni 0.2 O₂ and Li[Li 0.06 Na 0.07 K 0.07 Mn 0.6 Ni 0.2 O₂ respectively.

[0148] As shown in Figures 15-22, the S-LRMO active material has excellent performance and stability. In contrast to the rapid capacity decline and voltage decline shown by conventional Li-rich materials, almost no capacity decline was observed over many cycles.

[0149] Figure 23 is a graph of voltage vs. specific capacity showing the discharge rate data of the Li[Li 0.06 K 0.14 Mn 0.6 Ni 0.2 O₂ material. As shown in Figure 23, the material has high rate performance and has a capacity of about 180 mAh / g at the C / 2 rate. This good rate performance may be the result of the alkali atoms in the crystalline material forming a more facile lithium ion transport path within the system, enabling better conductivity and rate performance.

[0150] In particular, the S-LRMO active material exhibited stable capacity and voltage profiles, showing a significant improvement over conventional LRMO materials with similar compositions but that were not substituted or heat-treated (e.g., not rapidly quenched) as described above. Cells containing the S-LRMO active material exhibited specific capacities exceeding 260 mAh / g, such as 265-275 mAh / g at a C / 20 rate. As shown in Figure 16, Li 1.14 Na 0.06 Mn 0.6 Ni 0.2 Cells containing the O2 active material exhibited stable discharge specific capacity and charge / discharge efficiency over tens of cycles, demonstrating excellent stability and cycle life. Therefore, the S-LRMO active material indicates a loss of less than 10% of the average discharge voltage at the C / 20 rate after 200 charge / discharge cycles of a lithium-ion battery (e.g., less than 5%, less than 2%, or lower), and / or a capacity degradation of less than 5% over 200 C / 4 charge / discharge cycles of a lithium-ion battery (e.g., less than 3%, less than 2%, or lower), and / or a specific capacity of more than 200 mAh / g when charged and discharged at the C / 20 rate (e.g., more than 230 mAh / g, more than 250%, or higher), and / or a C / 2 discharge specific capacity of at least 75% of the C20 discharge specific capacity (e.g., at least 80%, at least 85%, at least 90%, or higher).

[0151] The X-ray data shown in Figures 11-14 demonstrate that high lithium substitution (e.g., at least 12.5%) allows the use of LRMO without significantly affecting its crystal structure or generating secondary crystalline phases. All of these X-ray diffraction patterns show only the expected lithium-rich crystalline phase structure, regardless of the type and amount of substitution material used. TEM / EDS data revealed that in this example with 5% Na substitution, Mn and Ni maintained a uniform spatial distribution throughout the sample.

[0152] Electrochemical test The synthesized cathode material was prepared by mixing Super-P carbon black and polyvinylidene fluroide (PVDF) in a ratio of 8:1.2:0.8, with the active material accounting for 80% of the total mass. The resulting mixture (blend) was then mixed with 15 ml of N-methyl-2-pyrrolidone for at least 1 hour, followed by two 10-minute sonication treatments. The resulting slurry was then mixed on a 100°C hot plate for at least 30 minutes, and spray-coated onto 10x10 cm, 10 μm thick aluminum foil heated to over 100°C. The foil was air-dried overnight in a 70°C oven and then punched out with a biopsy punch. Next, these punches were used to fabricate 2032 coin cells, each using lithium foil for the negative electrode, a 1.0 M LiPF650 / 50 ethylene carbonate / dimethyl carbonate solution for the electrolyte, a Celgard battery separator with a 0.5 mm stainless steel spacer, and a wave spring on the cathode side to ensure mechanical contact within the cell; each coin cell was assembled and sealed using a coin cell press in a dry, low-oxygen argon atmosphere.

[0153] For electrochemical performance investigations, a low-current Newware or Biologic battery tester was used to perform potential-limited galvanostatic testing on coin cells manufactured using the above process by applying a constant current. Under constant current charge-discharge conditions, the cells were cycled at a rate of C / 20 to C / 2 between 4.8 and 2V.

[0154] Figure 8A is a graph showing the cell potential versus capacitance, and Figure 8B shows the LRMO material (Li) that has not undergone microwave treatment or rapid quenching (in this case, relatively slow cooling on a metal plate). x (Mn y Ni 1-y ) 2-xThis is the specific capacity versus cycles for the comparative example O2 (where x=1.16 and y=0.7 in the equation). Referring to Figures 8A and 8B, it was found that the slowly cooled material had low capacity and capacity retention. After 50 full charge / discharge cycles (C / 2 rate), this material showed a specific capacity of 120 mAh / g at the C / 20 rate, which is far below the theoretical performance of this material. Furthermore, the material showed a significant voltage drop, with the average discharge potential falling below 3V after 30 cycles.

[0155] Figure 9A is a graph showing the cell potential-to-capacity ratio for exemplary cells containing LRMO active materials according to various embodiments of the present disclosure during the break-in cycle of the ultra-rapid quenching material; Figure 9B is a graph showing the cell potential-to-capacity ratio of the ultra-rapid quenching material over time; and Figure 9C is a graph showing the specific capacity-to-cycle ratio at the C / 20 rate over multiple cycles.

[0156] In contrast to the comparative materials shown in Figures 8A-8B, the exemplary LRMO cathode material fabricated using ultrarapid quenching, as shown in Figures 9A-9C, exhibited superior performance. The electrochemical performance data in Figures 9A and 9B demonstrated both (a) the ability to produce highly functional materials on a meaningful scale, and (b) that these materials possess performance characteristics comparable to or exceeding those of the much smaller batches produced. Notably, compared to materials fabricated using slower cooling methods, the voltage profile expands after the discharge capacity reaches approximately 100 mAh / g, exhibiting a desired inflection point. The voltage trace above this inflection point indicates virtually no “sag” or loss during the cycle, representing an improvement compared to materials fabricated using slower transfer techniques. This suggests that an ultrarapid cooling approach, involving gravity-driven transfer from the furnace to the quenching environment in less than 200 milliseconds, is desirable when combined with precursors rapidly decomposed via microwave irradiation.

[0157] Figure 10A is a graph showing the cell potential versus relative capacity of cells containing both materials that have undergone the quenching treatment described and those that have not. As shown in Figure 10B, which is a specific capacity versus cycle data set of materials treated with this processing tool, the quenched materials exhibit a significantly larger specific capacity and are extremely stable under cycling. TIFF2026513621000004.tif54164

[0158] While several embodiments of the present invention have been described and illustrated herein, those skilled in the art will readily conceive of various other means and / or structures for performing and / or obtaining the functions and / or one or more advantages described herein, and each of such variations and / or modifications will be considered within the scope of the present invention. More generally, those skilled in the art will readily understand that all parameters, dimensions, materials, and configurations described herein are illustrative, and that the actual parameters, dimensions, materials, and / or configurations will depend on the specific application or application in which the teachings of the present invention are used. Those skilled in the art will recognize or verify many equivalents to the specific embodiments of the present invention described herein without going beyond routine experimentation. Therefore, it should be understood that the embodiments described herein are presented only as examples, and within the scope of the appended claims and their equivalents, the present invention may be carried out in ways other than those specifically described and claimed. The present invention is directed toward the individual features, systems, articles, materials, and / or methods described herein. Furthermore, any combination of two or more such features, systems, articles, materials, and / or methods is included within the scope of the present invention, provided that they are not mutually inconsistent.

[0159] As used herein and in the claims, the expression “at least a portion” means a portion or all unless the opposite is clearly indicated. “At least a portion” may mean, according to a particular embodiment, at least 1% by weight, at least 2% by weight, at least 5% by weight, at least 10% by weight, at least 25% by weight, at least 50% by weight, at least 75% by weight, at least 90% by weight, at least 95% by weight, or at least 99% by weight, and / or, in a particular embodiment, up to 100% by weight.

[0160] In this specification and in the claims, the indefinite articles "a" and "an" should be understood to mean "at least one" unless the opposite meaning is explicitly indicated.

[0161] As used herein and in the claims, the expression “and / or” should be understood to mean “either one or both” of the elements thus combined, in other words, elements that exist in some cases as a combination and in other cases as separate elements. The other elements may be any other than those specifically identified by the “and / or” clause, regardless of whether they are related to or unrelated to the specifically identified elements unless the opposite meaning is explicitly indicated. Thus, as a non-restrictive example, when used with open-ended language such as “comprising,” a reference to “A and / or B” may, in one embodiment, refer to A without B (optionally including elements other than B); in another embodiment, refer to B without A (optionally including elements other than A); and in yet another embodiment, refer to both A and B (optionally including other elements), and so on.

[0162] Where used herein and in the claims, “or” should be understood to have the same meaning as “and / or” as defined above. For example, when separating items in a list, “or” or “and / or” should be interpreted as inclusive, in other words, including at least one of the number of elements or the list, but more than one, and optionally including additional items not on the list. Only terms that clearly indicate the opposite meaning, such as “one of,” “exactly one of,” or, as used in the claims, “consisting of,” refer to including exactly one of the number of elements or the list. Generally, where used herein, the term “or” should be interpreted as indicating an exclusive alternative (i.e., “one or the other but not both”) only when preceded by terms indicating exclusivity, such as “either,” “one of,” “only one of,” or “exactly one of.” As used in the claims, "consisting essentially of" shall have the ordinary meaning as it is used in the field of patent law.

[0163] As used herein and in the claims, the expression “at least one” referring to a list of one or more elements should be understood to mean at least one element selected from any one or more elements in the list of elements, but not necessarily including at least one of each element and all elements specifically enumerated in the list of elements, nor excluding any combination of elements in the list of elements. This definition also allows for the presence of elements other than those specifically identified in the list of elements to which the phrase “at least one” refers, whether related to or unrelated to the specifically identified elements. Therefore, as a non-restrictive example, "at least one of A and B" (or equivalently "at least one of A or B," or equivalently "at least one of A and / or B") could refer to, in one embodiment, one or more, optionally including A (optionally including elements other than B), where B is absent; in another embodiment, one or more, optionally including B (optionally including elements other than A); in yet another embodiment, one or more, optionally including A, and one or more, optionally including B (optionally including other elements); and so on.

[0164] Unless otherwise explicitly stated, the concentrations and percentages described herein are based on mass.

[0165] As used herein, "weight %" is an abbreviation for weight percentage. As used herein, "at %" is an abbreviation for atomic percentage.

[0166] Several embodiments can be embodied as methods, and various examples thereof have been described. The actions performed as part of the method can be ordered in any suitable manner. Thus, embodiments can be constructed in which actions are performed in a different order than illustrated, which include different actions (e.g., more or fewer) than those described, and / or which include performing several actions simultaneously, even though the embodiments described above show that the actions are performed sequentially.

[0167] In the claims, the use of ordinal terms such as “first,” “second,” and “third” to modify claim elements does not in itself imply priority, precedence, order, or temporal order in which the actions of a method are performed for one claim element relative to other claim elements, but is merely used as a label to distinguish a claim element having a particular name from other claim elements having the same name (but using ordinal terms).

[0168] Similar to the specification above, in the claims, all transitional expressions such as "comprising," "including," "carrying," "having," "containing," "involving," and "holding" are understood to be open-ended, meaning "not limited to but including." As specified in Section 2111.03 of the U.S. Patent and Trademark Office's Patent Examination Procedure Manual, only the transitional expressions "consisting of" and "consisting essentially of" are closed-ended or semi-closed-ended transitional expressions, respectively.

Claims

1. A heat treatment system, A furnace configured to sinter powder at a sintering temperature; A quenching device configured to rapidly cool at least a portion of a sintered powder in a quenching fluid; and A transfer conduit configured to supply at least a portion of a sintered powder having a sintering temperature from a furnace to a quenching device in 500 milliseconds or less. It consists of having, A heat treatment system configured such that the furnace agitates the powder for at least a portion of the time the powder is sintered.

2. The heat treatment system according to claim 1, wherein the furnace is a rotary furnace, a furnace configured to be agitated by vibration, and / or a fluidized bed furnace.

3. The heat treatment system according to claim 1, wherein the furnace is a rotary furnace.

4. The heat treatment system according to claim 3, wherein the furnace is a tilting rotary furnace.

5. A heat treatment system, A tilting rotary furnace configured to heat a powder to a first temperature; A quenching device configured to rapidly cool at least a portion of a heated powder in a quenching fluid of a second temperature; and A transfer conduit configured to supply at least a portion of a sintered powder having a sintering temperature from a tilting rotary furnace to a quenching device in 500 milliseconds or less. A heat treatment system comprising the following:

6. The quenching device is located below the furnace; and The heat treatment system according to any one of claims 1 to 5, wherein the transfer conduit comprises a substantially vertical tube connecting at least one outlet of the furnace to the inlet of the quenching device, and is configured to supply at least a portion of the sintered powder from the inclined rotary furnace to the quenching device at least partially by gravity.

7. The transfer conduit is configured to supply at least a portion of the sintered powder having a sintering temperature from the inclined rotary furnace to the quenching device at a quenching temperature that is 0°C to 200°C lower than the sintering temperature; and The heat treatment system according to claim 6, wherein the quenching device is configured to quench at least a portion of the powder from the quenching temperature to a temperature of 120°C or lower in 500 milliseconds or less.

8. The heat treatment system according to claim 7, wherein the quenching device is configured to quench at least a portion of the powder from the quenching temperature to room temperature in 500 milliseconds or less.

9. The heat treatment system according to claim 7, wherein the transfer conduit comprises an insulating material configured to limit the cooling of the powder, and a heater configured to heat the transfer conduit to at least a quenching temperature.

10. A heat treatment system according to any one of claims 7 to 9, wherein the sintering temperature is 800°C or higher and 1000°C or lower.

11. A heat treatment system according to any one of claims 7 to 10, wherein the sintering temperature is 850°C or higher and 1000°C or lower.

12. A heat treatment system according to any one of claims 3 to 11, wherein the rapid cooling temperature is 500°C or less.

13. The heat treatment system according to any one of claims 1 to 12, wherein the powder comprises lithium-rich metal oxide (LRMO) material powder.

14. A heat treatment system according to any one of claims 6 to 13, wherein at least a portion of the transfer conduit extends into the quenching device, and when a quenching fluid is present, an air seal is formed with the quenching fluid within the quenching device.

15. The heat treatment system according to any one of claims 1 to 14, wherein the quenching device includes a stirrer and a container configured to hold the quenching fluid when the quenching fluid is present.

16. The heat treatment system according to any one of claims 1 to 15, wherein the quenching device comprises a continuous liquid loop quenching device.

17. A heat treatment system according to any one of claims 1 to 16, wherein the quenching device comprises a quenching fluid.

18. The continuous liquid loop quenching system is A quenching conduit configured to receive at least a portion of the powder from a transfer conduit and, if a quenching fluid is present, to quench at least a portion of the powder in the quenching fluid; A separation container configured to separate at least a portion of the rapidly cooled powder from the rapidly cooled fluid; A pump configured to deliver a rapidly cooled fluid through a rapidly cooled conduit; and A return conduit configured to supply rapidly cooled fluid from the separation container to the pump. A heat treatment system according to any one of claims 16 to 17, comprising:

19. The continuous liquid loop quenching system is A quenching conduit configured to receive at least a portion of the powder from a transfer conduit and, if a quenching fluid is present, to quench at least a portion of the powder in the quenching fluid; A separation vessel comprising a batch or continuous centrifuge configured to receive at least a portion of the rapidly cooled powder and rapidly cooled fluid; A pump configured to deliver a rapidly cooled fluid through a rapidly cooled conduit; and A return conduit configured to supply rapidly cooled fluid from the centrifuge's holding container to the pump. It consists of having, The heat treatment system according to any one of claims 16 to 18, wherein the centrifuge is configured to separate at least a portion of the rapidly cooled powder and to send the rapidly cooled fluid to a holding container for collection, and the holding container is configured to pump at least a portion of the rapidly cooled fluid back to a rapidly cooled conduit.

20. The furnace, A process conduit having an inlet and an outlet; A drum configured to house process conduits and to heat process conduits to a sintering temperature; and A motor configured to rotate at least the process conduit. It consists of having, The heat treatment system according to any one of claims 1 to 19, wherein the process conduit is configured to transport powder through a furnace.

21. The heat treatment system according to claim 20, wherein the furnace has a base that supports a drum at a non-zero angle with respect to the horizontal direction such that the inlet of the process conduit is higher than the outlet of the process conduit, which is fluidly connected to the inlet of the transfer conduit.

22. The heat treatment system according to any one of claims 20 to 21, wherein the outlet of the process conduit has a plurality of openings arranged in an annular pattern around the side wall of the process conduit and extending through the side wall of the drum to the inlet of the transfer conduit.

23. Sintering powder at a sintering temperature inside a furnace; Stirring at least a portion of the powder during sintering; and At least a portion of the sintered powder having a sintering temperature is supplied, at least partially, from the furnace through a transfer conduit to the quenching fluid in the quenching device by gravity in 500 milliseconds or less. A method comprising [a certain element].

24. The method according to claim 23, wherein stirring is performed via rotation of at least a portion of the furnace, via vibration, and / or via the formation of a fluidized bed.

25. The method according to claim 23, wherein the stirring is performed via the rotation of at least a portion of the furnace.

26. The method according to claim 25, wherein the furnace is a tilting rotary furnace.

27. Sintering powder at a sintering temperature in an inclined rotary furnace; and At least a portion of the sintered powder having a sintering temperature is supplied from the inclined rotary furnace to the quenching fluid in the quenching device via a transfer conduit, at least partially by gravity, in 500 milliseconds or less. A method comprising [a certain element].

28. The method according to any one of claims 23 to 27, wherein each particle of the powder undergoes essentially the same rapid cooling thermal profile.

29. The quenching device is located below the furnace; and The method according to any one of claims 23 to 27, wherein the transfer conduit comprises a substantially vertical tube connecting at least one outlet of the furnace to the inlet of the quenching device.

30. The method according to any one of claims 23 to 29, wherein at least a portion of a sintered powder having a sintering temperature is supplied from a furnace into a quenching fluid in a quenching device at a quenching temperature that is 0°C or more and 200°C or less lower than the sintering temperature.

31. The method according to claim 30, wherein at least a portion of the powder is rapidly cooled in a rapidly cooling liquid from the rapidly cooling temperature to room temperature in 500 milliseconds or less.

32. The method according to any one of claims 30 to 31, wherein the transfer conduit comprises an insulating material for limiting the cooling of the powder, and a heater for heating the transfer conduit to at least a rapid cooling temperature.

33. The method according to any one of claims 23 to 32, wherein the sintering temperature is 800°C or more and 1000°C or less.

34. The method according to any one of claims 23 to 33, wherein the sintering temperature is 850°C or higher and 1000°C or lower.

35. The method according to any one of claims 30 to 34, wherein the rapid cooling temperature is 800°C or higher.

36. The method according to any one of claims 23 to 35, wherein the powder comprises a lithium-rich metal oxide (LRMO) material powder.

37. The method according to any one of claims 29 to 36, wherein the transfer conduit forms an air seal with the rapidly cooled fluid in the rapidly cooling device.

38. The method according to any one of claims 23 to 27, wherein the quenching device comprises a stirrer and a container containing a quenching fluid.

39. The method according to claim 27, wherein the quenching device comprises a continuous liquid loop quenching device.

40. The continuous liquid loop quenching system is A quenching conduit that receives at least a portion of the powder from a transfer conduit so that at least a portion of the powder is quenched in a quenching fluid; A separation container for separating rapidly cooled powder from a rapidly cooled fluid; A pump that delivers rapidly cooled fluid through a rapidly cooled conduit; and Return conduit that supplies rapidly cooled fluid from the separation container to the pump. The method according to claim 39, comprising:

41. The continuous liquid loop quenching system is A quenching conduit configured to receive at least a portion of the powder from a transfer conduit and to quench at least a portion of the powder in a quenching fluid; A separation vessel comprising a batch or continuous centrifuge configured to receive at least a portion of the rapidly cooled powder and rapidly cooled fluid; A pump configured to deliver a rapidly cooled fluid through a rapidly cooled conduit; and A return conduit configured to supply rapidly cooled fluid from the centrifuge's holding container to the pump. It consists of having, The method according to claim 39, wherein the centrifuge is configured to separate at least a portion of the rapidly cooled powder and to send the rapidly cooled fluid to a holding container for collection, and the holding container is configured to pump at least a portion of the rapidly cooled fluid back to a rapidly cooled conduit.

42. The furnace is: A process conduit having an inlet and an outlet; A drum for housing the process conduit and heating the process conduit to the sintering temperature; and At least a motor that rotates the process conduit It consists of having, The method according to claim 27, wherein the process conduit transports the powder through a rotary furnace.

43. The method according to claim 42, wherein the furnace has a base that supports a drum at a non-zero angle with respect to the horizontal direction such that the inlet of the process conduit is higher than the outlet of the process conduit, which is fluidly connected to the inlet of the transfer conduit.

44. The method according to any one of claims 42 to 43, wherein the outlet of the process conduit has a plurality of openings arranged in an annular pattern around the side wall of the process conduit and extending through the side wall of the drum to the inlet of the transfer conduit.

45. The heat treatment system according to any one of claims 1 to 22, wherein the powder is heated to a temperature sufficient to promote a relatively high degree of atomic disorder in the powder material.

46. The heat treatment system according to any one of claims 1 to 22 and 45, wherein the quenching device is configured such that at least a portion of the particles in the quenching device undergo substantially the same temperature change over time.

47. The heat treatment system according to any one of claims 1 to 22 and 45 to 46, wherein the furnace further has an outlet port position such that the heated powder particles exit the furnace at the heated temperature before entering the rapidly cooled liquid.

48. The heat treatment system according to claim 47, wherein the outlet port is located within the high-temperature zone of the furnace.

49. The heat treatment system according to claim 6, wherein the vertical tube is hermetically sealed.

50. A heat treatment system according to any one of claims 1 to 22 and 45 to 49, wherein a rapidly cooled powder forms a slurry suitable for transport from a rapidly cooled environment.

51. A heat treatment system according to any one of claims 1 to 22 and 45 to 50, further comprising a slurry pump.

52. The method according to any one of claims 23 to 44, wherein the transfer time through the transfer conduit is 200 milliseconds or less.

53. The method according to any one of claims 23 to 44 and 52, wherein the transfer time through the transfer conduit is 100 milliseconds or less.

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