Lithium-containing nanopowder, mechanical alloying alloy, or combination thereof, methods for manufacturing them, and manufacturing systems.

Abstract

One general aspect of the present disclosure is directed to a method for producing a lithium-containing nanopowder. An additional general aspect of the present disclosure is directed to a system for producing a lithium-containing nanopowder. A further general aspect of the present disclosure is directed to a lithium-containing nanopowder. A further general aspect of the present disclosure is directed to converting metals, metal oxides, or combinations thereof into a mechanically alloyed alloy using the disclosed manufacturing methods and manufacturing systems. The mechanically alloyed alloy can be a powder, e.g., a nanopowder, and may or may not include a lithium-containing nanopowder.

Description

Technical Field

[0001] The present disclosure relates to lithium-containing nano powders, mechanically alloyed (by) alloys, or combinations thereof. The present disclosure further relates to methods and systems used to manufacture lithium-containing nano powders, mechanically alloyed alloys, or combinations thereof.

Background Art

[0002] Lithium-containing materials and other types of mechanically alloyed alloys are used in several industries, including the emerging field of all-solid-state batteries that use lithium-containing materials as materials for anodes, cathodes, and solid electrolytes. Lithium-containing materials for solid electrolytes can be obtained as microscopic powders. These microscopic lithium-containing powders can be sintered to form anodes, cathodes, or solid electrolytes. However, sintered solid electrolytes made from currently available microscopic lithium-containing powders may be prone to forming dendritic crystals during battery operation.

[0003] To reduce the likelihood of dendritic crystal formation, ideally, the particle size of the lithium-containing material should be made even smaller beyond the microscopic scale. However, there are several technical obstacles to this. One is that as the lithium-containing material becomes smaller during the size reduction process, the reduced size increases the likelihood that the lithium-containing material will accumulate on the surface of the size reduction device. Also, in the size reduction process (e.g., the grinding process), a significant amount of heat may be generated. This can cause the temperature of the process to approach the melting point of lithium, and as a result, the lithium-containing material may partially or completely liquefy.

[0004] Attempts have been made to reduce the particle size of the lithium-containing material by introducing a liquid, such as a liquid solvent, into the size reduction process. However, this may introduce impurities into the lithium-containing material, and the removal of these impurities may be costly. [Overview of the project] [Problems that the invention aims to solve]

[0005] Therefore, improved lithium-containing nanopowder and improved methods and systems for producing it are needed. [Means for solving the problem]

[0006] The embodiments covered are defined by the claims, not by this summary. This summary is a high-level overview of various embodiments and introduces some of the concepts that are further explained in the "Detailed Description" section below. This summary is not intended to identify any significant or essential features of the claimed subject matter, nor is it intended to be used alone to determine the scope of the claimed subject matter. The subject matter should be understood by referring to the entire specification, any or all of the drawings, and the appropriate parts of each claim.

[0007] A general aspect of this disclosure relates to a method for producing lithium-containing nanopowder. In some specific non-limiting examples, the method may include grinding a lithium-containing material with a grinder while the grinder is in a first arrangement, rotating the grinder so that the grinder is in a second arrangement, stirring the lithium-containing material, cooling the lithium-containing material, returning the grinder to the first arrangement, and repeating the grinding, rotating, stirring, cooling, and returning until the lithium-containing material is converted into lithium-containing nanopowder.

[0008] A further general aspect of the present disclosure relates to a method for producing a mechanical alloying alloy from multiple metals, multiple metal oxides, or combinations thereof using the method steps described above.

[0009] A further general aspect of the present disclosure relates to a system for producing lithium-containing nanopowder. In some specific non-limiting examples, the system may include a grinding device, a stirring device configured to agitate the lithium-containing material inside the grinding device, and a cooling device configured to cool the lithium-containing material inside the grinding device.

[0010] A more general aspect of this disclosure relates to lithium-containing nanopowder. In some specific non-limiting examples, the lithium-containing nanopowder may include lithium and at least one additional element selected from at least one transition metal, at least one rare earth metal, at least one nonmetallic element, or any combination thereof.

[0011] The embodiments covered are defined by the claims, not by this summary. This summary is a high-level overview of various embodiments and introduces some of the concepts that are further described in the following “Detailed Description” section. This summary is not intended to identify any significant or essential features of the claimed subject matter, nor is it intended to be used alone to determine the scope of the claimed subject matter. The subject matter should be understood by referring to the entire specification, any or all of the drawings, and the appropriate parts of each claim. [Brief explanation of the drawing]

[0012] [Figure 1] The following are non-limiting examples of the particle size of lithium-containing nanopowder according to some aspects of this disclosure. [Figure 2] The following are non-limiting examples of the particle size of lithium-containing nanopowder according to some aspects of this disclosure. [Figure 3] The following are non-limiting examples of the particle size of lithium-containing nanopowder according to some aspects of this disclosure. [Modes for carrying out the invention]

[0013] Some embodiments of the present disclosure are described herein merely as examples with reference to the accompanying drawings. Particularly with reference to the drawings in detail hereof, it is emphasized that the illustrated embodiments are illustrative and intended to provide a schematic overview of embodiments of the present disclosure. In this regard, the description accompanied by the drawings will make it clear to those skilled in the art how embodiments of the present disclosure may be carried out.

[0014] A general aspect of this disclosure relates to a method for producing lithium-containing nanopowder from a lithium-containing material. As used herein, “lithium-containing material” is a material containing lithium. As used herein, “nanopowder” is a powder having an average particle size of 1 nm to 1000 nm. As used herein, “average particle size” can refer to particle radius, particle diameter, particle length, particle width, particle depth, or any combination thereof. As used herein, “lithium-containing nanopowder” is a nanopowder containing lithium.

[0015] In some examples, lithium-containing materials may include lithium and at least one additional element. In certain examples, the at least one additional element may be multiple additional elements. In some examples, one or more additional elements may be selected from at least one transition metal, at least one rare earth metal, at least one nonmetallic element, or any combination thereof. In certain embodiments, the additional elements may include at least one transition metal, at least one nonmetallic element, and at least one rare earth metal. In some embodiments, the at least one transition metal may be zirconium, titanium, manganese, nickel, cobalt, aluminum, iron, copper, gold, silver, platinum, palladium, or any combination thereof. In certain examples, the rare earth metal may be lanthanum, yttrium, cerium, neodymium, or any combination thereof. In some examples, the at least one nonmetallic element may include oxygen, phosphorus, carbon, sulfur, carbon, silicon, or any combination thereof.

[0016] Some specific examples of suitable lithium-containing materials include, but are not limited to, lithium lanthanum zirconium oxide (LLZO), lithium titanate (LTO), carbon-coated LTO, lithium manganese oxide (LMO), lithium nickel cobalt aluminum oxide (NA), lithium manganese nickel oxide (LMNO), LATP-coated lithium manganese nickel oxide, lithium lanthanum titanate, aluminum-doped lithium lanthanum zirconium oxide, lithium aluminum titanium phosphate, lithium cobalt oxide (LCO), lithium nickel manganese cobalt oxide, lithium iron phosphate, lithium 2.6 copper 0.4 N, lithium 2.6 cobalt 0.2 copper 0.2, or combinations thereof.

[0017] In certain embodiments, the lithium-containing material is loaded into a grinding device as a powder. The powder can be microparticles. As used herein, “microparticles” is powder having an average particle size of 1 micron or larger. In some examples, the average particle size of microparticles is not necessarily limited and can be, for example, 1-1000 microns, 10-1000 microns, 50-1000 microns, 100-1000 microns, 500-1000 microns, 1-500 microns, 1-100 microns, 1-50 microns, 1-10 microns, 50-500 microns, 10-100 microns, or any combination thereof. In some embodiments, microparticles may include macroscopic particles. As used herein, “macroscopic particles” is particles having an average particle size of 1 millimeter or larger.

[0018] In some embodiments, the lithium-containing material subjected to grinding consists of microscopic LLZO powder, or is essentially composed of microscopic LLZO powder, including microscopic LLZO powder. In some embodiments, the lithium-containing material does not contain any chemical elements other than lithium, lanthanum, zirconium, or oxygen.

[0019] In some examples, lithium-containing materials can be synthesized within the grinding apparatus during operation. This can occur by the formation of a mechanical alloy within the grinding apparatus. The synthesis of lithium-containing materials within the grinding apparatus can be carried out using multiple metals, multiple metal oxides, or combinations thereof in some implementations. In one particular example, the lithium-containing material is LLZO, which can be formed as a mechanical alloy within the grinding apparatus using, for example, lithium oxide, lanthanum oxide, and zirconium oxide. In one non-limiting embodiment, lithium oxide, lanthanum oxide, and zirconium oxide can be added to the grinding apparatus in a weight ratio of 3.5:1.5:2.

[0020] In some examples, a series of cations can be added to a grinding device as dopants to stabilize lithium-containing materials and improve ionic conductivity. In some embodiments, the series of cations may include Fe 3+ , Al 3+ , Ga 3+ Nb 4+ Ta 5+ Te 6+ This may include, but is not limited to, any combination thereof, of these methods. A specific example of the method may include adding an excess of lithium to the lithium-containing material during the method.

[0021] In some examples, this method can be used to synthesize a wide range of materials other than lithium-containing materials. This can be achieved by adding multiple metals, multiple metal oxides, or combinations thereof to a grinding device to form mechanical alloying alloys, as described above. This wide range of materials may include, but is not limited to, bismuth-containing alloys, antimony-containing alloys, transition metal carbides, iron-containing alloys, nickel-containing alloys, or any combination thereof. In certain embodiments, the mechanical alloying alloy may be mechanical alloying alloy powder. The mechanical alloying alloy powder may further be mechanical alloying alloy nanopowder. The mechanical alloying alloy nanopowder may have an average particle size in the same range as the average particle size of any embodiment of the lithium-containing nanopowder described herein.

[0022] This method may further include grinding a lithium-containing material using a grinding apparatus. The grinding apparatus can be any grinding apparatus known in the art. For example, the grinding apparatus may be a rod mill, a self-sharpening mill, a semi-sharpening (SAG) mill, a pebble mill, or a vertical shaft impactor (VSI) mill. In a particular embodiment, the grinding apparatus may include a grinding chamber and a plurality of grinding media. In a particular embodiment of this disclosure, the grinding chamber may be a milling pot. The milling pot may be a ceramic milling pot. The ceramic milling pot may contain some or all of the same elements as the lithium-containing material. This may reduce the possibility of introducing impurities into the method. The ceramic milling pot may contain a variety of materials, including but not limited to zirconium oxide, aluminum oxide, LLZO, or any combination thereof. The milling pot may be a polymer milling pot. The polymer milling pot may, for example, be polyurethane or epoxy. In some implementations, the grinding apparatus is a ball mill, and the grinding media are grinding balls. In some cases, the crushed balls may contain at least one element common to the lithium-containing material. This may also reduce the possibility of impurities being introduced during the process.

[0023] In some cases, grinding lithium-containing materials may involve rotating the grinder around its axis. In some cases, rotating the grinder around its axis allows multiple grinding media to repeatedly come into contact with the lithium-containing material, thereby reducing the size of the lithium-containing material. In cases where the grinder is a ball mill, multiple grinding balls can repeatedly come into contact with the lithium-containing material, thereby reducing the size of the lithium-containing material.

[0024] In some examples, grinding is performed by rotating the grinding device at a certain rotational speed. In some embodiments, the rotational speed of the grinding device can be in the range of 100 rpm to 3000 rpm, 500 rpm to 3000 rpm, 1000 rpm to 3000 rpm, 2000 rpm to 3000 rpm, 100 rpm to 2000 rpm, 100 rpm to 1000 rpm, 100 rpm to 500 rpm, 500 rpm to 2000 rpm, 500 rpm to 1000 rpm, 1000 rpm to 2000 rpm, or any combination thereof.

[0025] In some embodiments, the grinding of lithium-containing materials can be performed while the grinding apparatus is in a first arrangement. In some implementations, the first arrangement is a vertical arrangement. However, in certain embodiments, the first arrangement may be a horizontal arrangement. Furthermore, the vertical arrangement can be inverted (i.e., "upside down") or upright.

[0026] In some embodiments, this method may further include rotating the grinder so that it is in a second configuration. In some implementations, the second configuration is a horizontal configuration. However, in certain embodiments, the second configuration may be a vertical configuration. In certain embodiments, rotating the grinder may include rotating the grinder by 90° (for example, by rotating the grinder sideways). The grinder can be rotated clockwise or counterclockwise without limitation. The grinder can also be rotated continuously or periodically.

[0027] In certain cases, this method may include stirring the grinding device. Stirring can be done, for example, by striking or shaking the grinding device.

[0028] In some examples, agitating the lithium-containing material inside the grinding apparatus may include striking the grinding apparatus with an agitator. In certain embodiments, the agitator may include an impact rod. The impact rod can agitate the grinding apparatus by moving in multiple directions (e.g., upward and downward). The impact rod can also agitate the grinding apparatus by vibrating while in contact with it. In some examples, the impact rod vibrates and moves simultaneously in multiple directions, thereby agitating the grinding apparatus. The agitation may be performed when the grinding apparatus is in a second configuration, which may optionally be in a horizontal configuration.

[0029] The arrangement of the agitator is not limited, as long as the agitator is within striking distance of the grinder. As used herein, “within striking distance” means that the agitator is at a sufficient distance from the grinder to agitate it. For example, the agitator may be inside the grinder (top, bottom, or side), outside the grinder, or any combination thereof. In some embodiments, the agitator may include multiple components (e.g., multiple impact rods). In certain embodiments, one component of the agitator (e.g., one impact rod) may be inside the grinder, while another component of the agitator (e.g., a second impact rod) may be outside the grinder. In some examples, the first and second components can agitate the grinder continuously. In some embodiments, the first and second components can agitate the grinder simultaneously.

[0030] Certain embodiments of this method include agitating the grinder by rotating it around its axis. Agitation by rotation may be performed when the grinder may be in a second configuration (possibly a horizontal configuration). Agitation by rotation may also be performed simultaneously with or in conjunction with other forms of agitation, such as during impact of the grinder by an impact rod.

[0031] The stirring of the grinding apparatus by rotation may be performed at a rotational speed slower than the rotational speed during the grinding step. For example, the rotational speed during stirring can be in the range of 5 rpm to 500 rpm, 50 rpm to 500 rpm, 100 rpm to 500 rpm, 100 rpm to 500 rpm, 200 rpm to 500 rpm, 300 rpm to 500 rpm, 400 rpm to 500 rpm, 5 rpm to 400 rpm, 5 rpm to 300 rpm, 5 rpm to 200 rpm, 5 rpm to 100 rpm, 5 rpm to 50 rpm, 50 rpm to 400 rpm, 100 rpm to 300 rpm, 100 rpm to 200 rpm, 200 rpm to 300 rpm, or any combination thereof.

[0032] Some embodiments of the method may include cooling the lithium-containing material inside the grinding apparatus. Cooling the lithium-containing material inside the grinding apparatus can be done while the grinding apparatus is in a second arrangement, possibly a horizontal arrangement. In certain examples, cooling the lithium-containing material inside the grinding apparatus can be done by bringing the grinding apparatus into contact with a cooling medium. The cooling medium can be any suitable cooling medium and can be solid, liquid, or gas. In some specific examples, the cooling medium may include water. In further embodiments, the cooling medium may include at least one refrigerant.

[0033] In certain embodiments, cooling the lithium-containing material inside the grinding apparatus may include bringing the grinding apparatus into direct contact with a cooling medium. For example, bringing the grinding apparatus into direct contact with a cooling medium may include using a nozzle to spray the cooling medium into the area surrounding the grinding apparatus. When the cooling medium is sprayed into the area surrounding the grinding apparatus using a nozzle, the cooling medium comes into direct contact with the outside of the grinding apparatus, thereby cooling the lithium-containing material inside the grinding apparatus.

[0034] Cooling the lithium-containing material inside the grinding apparatus may, in some cases, involve indirectly bringing the grinding apparatus into contact with a cooling medium. In certain exemplary embodiments, indirect contact of the grinding apparatus with a cooling medium may involve circulating the cooling medium through a cooling jacket surrounding the grinding apparatus.

[0035] In certain embodiments, this method may include returning the grinding device to a first configuration. Returning the grinding device to a first configuration may include rotating the grinding device in the opposite direction to the rotation step. For example, if the grinding device rotates 90° clockwise during the rotation step, the grinding device may rotate 90° counterclockwise during the step of returning the grinding device to a first configuration. Similarly, if the grinding device rotates 90° counterclockwise during the rotation step, the grinding device may rotate 90° clockwise during the step of returning the grinding device to a first configuration. As described above, the first configuration may be vertical or horizontal.

[0036] In certain embodiments, some or all of the method steps can be repeated until the lithium-containing material is converted into lithium-containing nanopowder. The method steps can be repeated once or more times. In some embodiments, the grinding step, the rotating step, the stirring step, the cooling step, and the returning step may be repeated.

[0037] In some examples, some or all of the method steps can be repeated until the lithium-containing nanopowder reaches the target average particle size. For example, the target average particle size can be 1nm-500nm, 5nm-500nm, 10nm-500nm, 25nm-500nm, 50nm-500nm, 75nm-500nm, 100nm-500nm, 1nm-100nm, 1nm-75nm, 1nm-50nm, 1nm-25nm, 1nm-10nm, 1nm-5nm, 5nm-100nm, 10nm-75nm, 25nm-50nm, or any combination thereof.

[0038] In certain examples, during the method, the temperature inside the grinding apparatus is maintained below the melting point of lithium, which is 180°C. In some embodiments, the temperature inside the grinding apparatus is maintained at room temperature, which is 20°C to 30°C as defined herein. In some embodiments, the temperature inside the grinding apparatus can be maintained within a variety of temperature ranges, including but not limited to, 20°C to 180°C, 40°C to 180°C, 60°C to 180°C, 80°C to 180°C, 100°C to 180°C, 120°C to 180°C, 140°C to 180°C, 160°C to 180°C, 20°C to 160°C, 20°C to 140°C, 20°C to 120°C, 20°C to 100°C, 20°C to 80°C, 20°C to 60°C, 20°C to 40°C, 40°C to 160°C, 60°C to 140°C, 80°C to 120°C, or combinations thereof.

[0039] In some embodiments, the method does not involve contacting the lithium-containing material with a liquid. In certain examples, the method does not involve contacting the lithium-containing material with a solvent. Some examples of solvents that may be excluded from some methods of this disclosure include, but are not limited to, organic solvents, including alcohols. In some embodiments, a grinding apparatus (e.g., a milling pot) may be sealed with gas throughout the method. The gas may be an inert gas. The inert gas may be, for example, nitrogen or a noble gas (e.g., xenon or argon).

[0040] In certain embodiments, this method improves the production yield of lithium-containing nanopowder. In some embodiments, the improved production yield may be 98% to 100%, 99% to 100%, 99.5% to 100%, 99.95% to 100%, 99.995% to 100%, 99.9995% to 100%, or any combination thereof.

[0041] Some non-limiting aspects of this disclosure relate to systems for producing lithium-containing nanopowder. In certain examples, the system can be used to carry out the above method. In some examples, the system may include the above-described grinding apparatus. In certain implementations, the system may include the above-described stirring apparatus. The stirring apparatus may be configured to stir the lithium-containing material inside the grinding apparatus. In some cases, the system may include a cooling apparatus. The cooling apparatus may be configured to cool the lithium-containing material inside the grinding apparatus.

[0042] The above steps can be repeated until the lithium-containing material 6 is converted into lithium-containing nanopowder having the target average particle size.

[0043] Some aspects of this disclosure may relate to lithium-containing nanopowder. In some specific non-limiting examples, lithium-containing nanopowder may consist of, or be essentially composed of, lithium and at least one additional element. In some specific non-limiting examples, lithium-containing nanopowder may consist of, or be essentially composed of, lithium and several additional elements. One or more additional elements may consist of, or be essentially composed of, at least one transition metal, at least one rare earth metal, at least one nonmetallic element, or any combination thereof. In some specific non-limiting examples, lithium-containing nanopowder may consist of, or be essentially composed of, LLZO nanopowder, including LLZO nanopowder.

[0044] In certain implementations, the lithium-containing material may be the same as or different from the examples of lithium-containing materials described above. In some examples, at least one transition metal, at least one rare earth metal, at least one nonmetallic element, or any combination thereof may be the same as those disclosed above. In some examples, at least one transition metal, at least one rare earth metal, at least one nonmetallic element, or any combination thereof may be different from those disclosed above.

[0045] In some embodiments, lithium-containing nanopowder may have a specific average particle size. In some embodiments, lithium-containing nanopowder can be approximated as spherical using approximation methods known in the art. When lithium-containing nanopowder is approximated as spherical, the average particle size can be considered as the diameter of the lithium-containing nanopowder. Some examples of average particle sizes include 1 nm to 500 nm, 5 nm to 500 nm, 10 nm to 500 nm, 25 nm to 500 nm, 50 nm to 500 nm, 75 nm to 500 nm, 100 nm to 500 nm, 1 nm to 100 nm, 1 nm to 75 nm, 1 nm to 50 nm, 1 nm to 25 nm, 1 nm to 10 nm, 1 nm to 5 nm, 5 nm to 100 nm, 10 nm to 75 nm, 25 nm to 50 nm, or any combination thereof.

[0046] Further examples of average particle sizes are shown in Figures 1 to 3. Figure 1 shows an example of lithium-containing nanopowder particles captured using a transmission electron microscope (TEM). As shown in Figure 1, the particle diameter of the first example is 67.83 nm, while the particle diameter of the second example is 112.71 nm. Figures 2 and 3 show the particle distribution of a specific lithium-containing nanopowder according to this disclosure. As shown in Figure 2, an example of lithium-containing nanopowder can have an average particle size of 237 nm, as indicated by the peak in the particle size distribution in Figure 2. As shown in Figure 3, an example of lithium-containing nanopowder can have an average particle size of 14.4 nm, as indicated by the peak in the particle size distribution in Figure 3.

[0047] In some examples, the lithium-containing nano powder can have a specific particle density. For example, the lithium-containing nano powder can have a particle density of 0.5 g / cm 3 to 1 g / cm 3 , 0.6 g / cm 3 to 1 g / cm 3 , 0.7 g / cm 3 to 1 g / cm 3 , 0.8 g / cm 3 to 1 g / cm 3 , 0.9 g / cm 3 to 1 g / cm 3 , 0.5 g / cm 3 to 0.9 g / cm 3 , 0.5 g / cm 3 to 0.8 g / cm 3 , 0.5 g / cm 3 to 0.7 g / cm 3 , 0.5 g / cm 3 to 0.6 g / cm 3 , 0.6 g / cm 3 to 0.9 g / cm 3 , 0.7 g / cm 3 to 0.8 g / cm 3 , or can have a particle density of any combination thereof. In some further examples, the lithium-containing nano powder can have a particle density of 0.8 g / cm 3 to 0.9 g / cm 3 , 0.82 g / cm 3 to 0.9 g / cm 3 , 0.84 g / cm 3 to 0.9 g / cm 3 , 0.86 g / cm 3 to 0.9 g / cm 3 , 0.88 g / cm 3 to 0.9 g / cm 3 , 0.8 g / cm 3 to 0.88 g / cm<000004e>, 0.8 g / cm 3 to 0.86 g / cm 3 , 0.8 g / cm 3 to 0.84 g / cm 3 , 0.8 g / cm 3 to 0.82 g / cm 3 , 0.82 g / cm 3~0.88 g / cm³ 3 0.84 g / cm³ 3 ~0.86 g / cm³ 3 It can have particle densities of , or any combination thereof. In yet another example, lithium-containing nanopowder may have a density of 0.1 g / cm³. 3 ~5g / cm 3 , 0.2 g / cm³ 3 ~5g / cm 3 , 0.5 g / cm 3 ~5g / cm 3 , 1 g / cm³ 3 ~5g / cm 3 , 2g / cm³ 3 ~5g / cm 3 , 3g / cm³ 3 ~5g / cm 3 , 4g / cm³ 3 ~5g / cm 3 , 0.1 g / cm³ 3 ~4g / cm 3 , 0.1 g / cm³ 3 ~3g / cm 3 , 0.1 g / cm³ 3 ~2g / cm 3 , 0.1 g / cm³ 3 ~1g / cm 3 , 0.1 g / cm³ 3 ~1g / cm 3 , 0.1 g / cm³ 3 ~0.5g / cm 3 , 0.1 g / cm³ 3 ~0.2g / cm 3 , 0.2 g / cm³ 3 ~4g / cm 3 , 0.5 g / cm 3 ~3g / cm 3 , 1 g / cm³ 3 ~2g / cm 3 The particle density can be any combination of these.

[0048] In some implementations, lithium-containing nanopowder may exhibit a specific sintering temperature. As used herein, sintering temperature is the temperature required to form a solid mass from lithium-containing nanopowder by heat under ambient pressure without melting the nanopowder. Some specific examples of sintering temperatures include, but are not limited to, 500°C to 1250°C, 600°C to 1250°C, 700°C to 1250°C, 800°C to 1250°C, 1000°C to 1250°C, 1000°C to 1250°C, 500°C to 1000°C, 500°C to 800°C, 500°C to 700°C, 500°C to 600°C, 600°C to 1000°C, 700°C to 800°C, or combinations thereof.

[0049] In certain cases, lithium-containing nanopowder may exhibit a specific sintering time. As used herein, sintering time is the time required to form a solid mass from lithium-containing nanopowder by heat at the sintering temperature and ambient pressure specified herein, without melting the lithium-containing nanopowder. Some specific examples of sintering times include, but are not limited to, 0.3 to 10 hours, 0.5 to 10 hours, 1 to 10 hours, 2 to 10 hours, 4 to 10 hours, 6 to 10 hours, 8 to 10 hours, 0.3 to 8 hours, 0.3 to 6 hours, 0.3 to 4 hours, 0.3 to 2 hours, 0.3 to 1 hour, 0.3 to 0.5 hours, 0.5 to 8 hours, 1 to 6 hours, 2 to 4 hours, or any combination thereof.

[0050] In some cases, lithium-containing nanopowder has up to 2% by weight of impurities. In further cases, lithium-containing nanopowder has up to 1% by weight of impurities. In yet another case, lithium-containing nanopowder has up to 0.5% by weight of impurities. In yet another case, lithium-containing nanopowder has up to 0.1% by weight of impurities. In yet another case, lithium-containing nanopowder has up to 0.05% by weight of impurities. In yet another case, lithium-containing nanopowder has up to 0.01% by weight of impurities. In yet another case, lithium-containing nanopowder has up to 0.001% by weight of impurities.

[0051] Other purposes and advantages of the disclosed advantages and improvements will become apparent from the following description made in conjunction with the accompanying drawings. While detailed embodiments of the disclosed invention are disclosed herein, it should be understood that the disclosed embodiments are merely illustrative examples of the disclosed invention, which can be embodied in various forms. Furthermore, each of the examples given with respect to the various embodiments of the disclosed invention is for illustrative purposes only and not limiting.

[0052] Throughout this specification and the claims, the following terms have the meanings expressly associated herein unless the context clearly indicates otherwise. The phrases “in one embodiment,” “in one embodiment,” and “in some embodiments,” as used herein, may refer to the same embodiment, but not necessarily the same embodiment. Furthermore, the phrases “in another embodiment” and “in some other embodiments,” as used herein, may refer to a different embodiment, but not necessarily a different embodiment. All embodiments of this disclosure are intended to be combined without departing from the scope or spirit of this disclosure.

[0053] As used herein, the term “based on” is not exclusive and, unless otherwise clearly indicated by the context, may be based on additional elements not listed. Throughout this specification, the meanings of “a,” “an,” and “the” include multiple references. The meaning of “in” includes “in” and “on.”

[0054] All prior patents, publications, and test methods referenced herein are incorporated in their entirety by reference.

[0055] Variations, modifications, and alterations of the embodiments of the Disclosure described above will be obvious to those skilled in the art. All such variations, modifications, and alterations are intended to fall within the spirit and scope of the Disclosure, limited only by the appended claims.

[0056] While several embodiments of this disclosure have been described, these embodiments are illustrative and not limiting, and it will be understood that many modifications will be apparent to those skilled in the art. For example, all dimensions discussed herein are provided as examples only and are intended to be illustrative and not limiting.

[0057] Any configuration or element explicitly identified in this description may be specifically excluded as a configuration or element of one embodiment of the present invention as defined in the claims.

[0058] As used herein, the term “essentially derived from” limits the scope of a particular claim to a particular material or step, and any material or step that does not substantially affect one or more basic and novel features of the particular claim. In some embodiments, a claim described as “essentially derived from” may allow the addition of any undescribed component that does not substantially affect at least one of the sintering temperature, sintering time, average particle size, or particle density. In some embodiments, a claim described as “essentially derived from” may allow the addition of at least one additive, at least one filler, or any combination thereof.

[0059] The disclosures described herein can be implemented even without any one or more elements or limitations not specifically disclosed herein. Therefore, for example, in each example herein, any of the terms “including,” “essentially consisting of,” and “consisting of” can be replaced with any of the other two terms. The terms and expressions used are for illustrative purposes only and are not limiting; the use of such terms and expressions is not intended to exclude any equivalents of the illustrated and described configuration or part thereof, and it is recognized that various modifications are possible within the scope of this disclosure.

Claims

1. The process involves a step of grinding a microscopic lithium lanthanum zirconium oxide (LLZO) powder using a grinding device while the grinding device is in a first configuration, The step of rotating the pulverizing device to position it in a second configuration, The step of stirring the microscopic LLZO powder while the pulverizing device is in the second configuration, The steps include: cooling the microscopic LLZO powder while the pulverizing device is in the second configuration; The steps include returning the crushing device to the first configuration, The steps of grinding, rotating, stirring, cooling, and returning are repeated until the microscopic LLZO powder is converted into LLZO nanopowder. Methods that include...

2. The aforementioned grinding apparatus is The grinding chamber and Multiple crushing balls and The method according to claim 1, wherein the ball mill is equipped with the following features.

3. The method according to claim 1, wherein the microscopic LLZO powder has an average particle size of 1 to 1000 microns.

4. The method according to claim 1, further comprising the step of synthesizing the microscopic LLZO powder in the grinding apparatus using multiple metals, multiple metal oxides, or a combination thereof.

5. The method according to claim 1, wherein the step of grinding the microscopic LLZO powder includes the step of rotating the grinding device around the axis of the grinding device at a rotational speed of 100 rpm to 3000 rpm.

6. The method according to claim 1, wherein the first arrangement is a vertical arrangement.

7. The method according to claim 1, wherein the second arrangement is a horizontal arrangement.

8. The method according to claim 1, wherein the step of rotating the pulverizing device to the second arrangement includes the step of rotating the pulverizing device by 90°.

9. The method according to claim 1, wherein the step of returning the grinding device to the first arrangement includes the step of rotating the grinding device 90° in the opposite direction.

10. The method according to claim 1, wherein the LLZO nanopowder has an average particle size of 1 nm to 500 nm.

11. The method according to claim 1, wherein the temperature inside the grinding apparatus is in the range of 20°C to 180°C.

12. The method according to claim 1, wherein the step of stirring the microscopic LLZO powder inside the fine grinding apparatus includes the step of striking the grinding apparatus with an impact rod.

13. The method according to claim 1, wherein the step of stirring the microscopic LLZO powder includes the step of rotating the grinding device around the axis of the grinding device at a rotational speed of 5 rpm to 500 rpm.

14. The method according to claim 1, wherein the cooling step includes bringing the grinding device into direct contact with the cooling medium by spraying the cooling medium over an area surrounding the grinding device using a nozzle.

15. The method according to claim 1, wherein the cooling step includes the step of bringing the grinding device into indirect contact with the cooling medium by flowing the cooling medium through a cooling jacket surrounding the grinding device.

16. The method according to claim 1, wherein the method does not include the step of bringing the microscopic LLZO powder into contact with a liquid.

17. The method according to claim 1, wherein the method does not include the step of contacting the microscopic LLZO powder with a solvent.

18. The method according to claim 1, wherein the method yields a production yield of 98% to 100% of the LLZO nanopowder.

19. The method according to claim 1, wherein the LLZO nanopowder has an average particle size of 1 nanometer to 500 nanometers.

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