Pelletization for all-dry synthesis of lithium transition metal oxide materials

Abstract

Disclosed herein is a method of pelletization of precursor mixture before firing to produce lithium transition metal oxide positive electrode materials. The precursor mixture may include a stoichiometric amount of one or more transition metal feedstocks, one or more lithium sources, and one or more dopants that are combined in a liquid-free environment. The methods disclosed herein may involve the use of a substrate with a porosity as a firing substrate or tray. The pelletization methods herein enhance lithiation kinetics, reduce lithium loss, and improve the positive electrode material's charge and discharge characteristics.

Description

PELLETIZATION FOR ALL-DRY SYNTHESIS OF LITHIUM TRANSITIONMETAL OXIDE MATERIALSINCORPORATION BY REFERENCE TO RELATED APPLICATION

[0000] This PCT application claims priority to U.S. Provisional Application 63 / 549311, filed February 2, 2024, the entirety7of which is incorporated herein for any and all purposes.BACKGROUND OF THE DISCLOSUREField of the Disclosure

[0001] This disclosure relates to preparing lithium transition metal oxide positive electrode materials for lithium-ion batteries.Description of the Related Art

[0002] Rechargeable lithium-ion (Li-ion) batteries have emerged as a dominant technology in the field of electric vehicles and large-scale grid storage due to its high energydensity, excellent cycle life, and efficient energy output. Significant research efforts, both in academia and industry-, have been dedicated to improving capacity, energy density, power density, and cycle life to go beyond those commercially available. In addition, reducing the cost of Li-ion battery is also crucial and can be done mainly by optimizing cathode materials as they account for a significant portion of the battery- cost. Cathode materials must be prepared from inexpensive precursors with low-cost synthesis process.

[0003] Some methods of cathode material manufacture adopt precursors made from yvet co-precipitation process. The particle size, morphology-, transition metal distribution, and density can be tuned by optimizing synthesis parameters. However, for some materials, particularly those with high-Ni and low-Co compositions, large scale synthesis remains a challenge in a manufacturing level. Various critical parameters are different than the lab-scale synthesis, for example, transition metal diffusion, sintering atmosphere, side reactions, material homogeneity-, and reproducibility-.SUMMARY OF THE DISCLOSURE

[0004] In some embodiments the techniques described herein relate to a method of preparing a lithium transition metal oxide positive electrode material for a secondary batterycomprising: preparing a precursor mixture by mixing a stoichiometric amount of one or moretransition metal feedstocks, one or more lithium sources, and one or more dopants in a liquid- free environment; and pelletizing the precursor mixture into one or more pellets; and heating the pelletized precursor mixture on a substrate to produce lithium transitional metal oxide positive electrode material. The method may additionally comprise pulverizing the lithium transitional metal oxide positive electrode material, mixing the pulverized material with one or more coating materials or one or more additional lithium sources to produce a coated material, repelletizing the coated material to produce repelletized material, and reheating the repelletized material to produce a coated lithium transition metal oxide cathode material.

[0005] In some aspects, the techniques described herein relate to a method of preparing a lithium transition metal oxide positive electrode material for a battery', the method including: (a) preparing a precursor mixture by mixing a stoichiometric amount of one or more transition metal feedstocks, one or more lithium sources, and one or more dopants in a liquid- free environment; (b) pelletizing the precursor mixture into one or more pellets under pressures of at least about 0.1 MPa; and (c) heating the pelletized precursor mixture on a substrate to produce the lithium transitional metal oxide positive electrode material.

[0006] In some aspects, the techniques described herein relate to a method, wherein the one or more transition metal feedstocks and the one or more dopants are selected from the group consisting of: elemental metal, oxides, hydroxides, oxyhydroxides, carbonates, sulfates, nitrates, acetates, and combinations thereof.

[0007] In some aspects, the techniques described herein relate to a method, wherein the one or more lithium sources are selected from the group consisting of: Li carbonate, Li oxide, Li hydroxide, Li hydroxide monohydrate, Li acetate, Li chloride, Li fluoride, Li nitrate, Li sulfate, and mixtures thereof.

[0008] In some aspects, the techniques described herein relate to a method, wherein the one or more dopants are selected from the group consisting of: Na, B, Al, Mg, Zr, Nb, Fe, Si, P, Mo, Ba, Sr, Ca, Zn, Cr, V, W, Nd, La, Cs, Ta, Ce, Cu, Eu, Ti, Sn, Sb, Pb, Bi, Rb, and mixtures thereof.

[0009] In some aspects, the techniques described herein relate to a method, wherein the precursor mixture is pelletized using a hydraulic press.

[0010] In some aspects, the techniques described herein relate to a method, wherein the lithium transitional metal oxide positive electrode material is selected from the group consisting of NMC, NCA, LMO, LFP, LNMO, LMO, and LCO.

[0011] In some aspects, the techniques described herein relate to a method, wherein the pressure applied to the pelletized mixture through hydraulic press is in a range of about 0.1- 100 MPa.

[0012] In some aspects, the techniques described herein relate to a method, wherein the pellet is in the shape of a cylinder, sphere, cone, pyramid, prism, cuboid, cube, or a combination thereof.

[0013] In some aspects, the techniques described herein relate to a method, wherein the pellet has a porosity of about 5-90 % prior to the heating.

[0014] In some aspects, the techniques described herein relate to a method, wherein the substrate is porous ceramic saggar that has an apparent porosity ranging from about 0-50%.

[0015] In some aspects, the techniques described herein relate to a method, wherein heating the pelletized precursor mixture is carried out under an atmosphere of inert gas, oxygen, a reduced oxygen partial pressure gas, dry air, or air.

[0016] In some aspects, the techniques described herein relate to a method, wherein the heating temperature is in a range between about 450-1100 °C.

[0017] In some aspects, the techniques described herein relate to a method, wherein heating is carried out with one or more temperature holds.

[0018] In some aspects, the techniques described herein relate to a method, additionally including pulverizing the heated pelletized precursor mixture through at least one of impact milling, jet milling, or grinding to produce pulverized material.

[0019] In some aspects, the techniques described herein relate to a method, wherein the method further includes mixing the pulverized material with one or more coating materials or one or more additional lithium sources to produce coated material.

[0020] In some aspects, the techniques described herein relate to a method, wherein the method further includes repelletizing the coated material to produce repelletized material.

[0021] In some aspects, the techniques described herein relate to a method, wherein the method further includes reheating the repelletized material.

[0022] In some aspects, the techniques described herein relate to a Li-ion battery including an electrode material including: a lithium transition metal oxide material produced from the methods disclosed herein.

[0023] In some aspects, the techniques described herein relate to an all-dry method for preparing a positive electrode material for a battery, the method including: preparing a precursor mixture by mixing a stoichiometric amount of nickel, manganese, and copper metal feedstocks, one or more lithium sources, and, optionally, one or more dopants in a liquid-freeenvironment; mechanically compressing the precursor mixture into a compressed material having a porosity of about 5-90 %; and heating the compressed precursor mixture at temperatures exceeding 700 degrees Celsius to produce the positive electrode material.

[0024] In some aspects, the techniques described herein relate to a method, wherein the one or more dopants are present and are selected from the group consisting of: Na, B, Al, Mg, Zr, Nb, Fe, Si, P, Mo, Ba, Sr, Ca, Zn, Cr, V. W, Nd, La, Cs, Ta, Ce, Cu, Eu, Ti, Sn, Sb, Pb. Bi. Rb. and mixtures thereof.

[0025] In some aspects, the techniques described herein relate to a method, wherein the one or more dopants include Zr.

[0026] In some aspects, the techniques described herein relate to a method, wherein the positive electrode material consists essentially of particles that have single crystal morphology.

[0027] In some aspects, the techniques described herein relate to a method, wherein the positive electrode material consists essentially of particles that have uniform particle size without deagglomeration.

[0028] In some aspects, the techniques described herein relate to a method, wherein the one or more dopants are present and are configured to limit transition metal interdiffusion.

[0029] In some aspects, the techniques described herein relate to a method, wherein the positive electrode material has a porosity less than about 30%.

[0030] In some aspects, the techniques described herein relate to a pelletized cathode formulation including: a pellet containing a precursor mixture with a stoichiometric amount of one or more transition metal feedstocks, one or more lithium sources, and, optionally, one or more dopants; wherein the pellet is substantially free of solvents and solvent residues; wherein the pellet has a porosity less than about 70%; wherein the porosity of the pellet is calculated from the following equation:Bulk densityPorosity = 1 — ( Particle density where bulk density7is mass of the pellet per given volume and particle density is calculated from the theoretical mass density of the precursor mixture.

[0031] In some aspects, the techniques described herein relate to a pelletized cathode formulation, wherein the pellet contains a stoichiometric amount of lithium, nickel, manganese, and cobalt for an Li[NiMnCo] cathode material.

[0032] In some aspects, the techniques described herein relate to a pelletized cathode formulation, wherein the pellet is free of iron.

[0033] In some aspects, the techniques described herein relate to a pelletized cathode formulation, wherein the pelletized cathode formulation includes zirconium.

[0034] In some aspects, the techniques described herein relate to a pelletized cathode formulation, wherein the pellet contains a stoichiometric amount of materials represented by the formula: Lii+x[(NinMnmCoc)i-aAa]i-xO2; where: -0.03 < x < 0.06; n + m + c = 1; n > 0.05; m > 0.05; c > 0.05; A is a metal dopant; and 0 < a < 0.05.

[0035] In some aspects, the techniques described herein relate to a pelletized cathode formulation, wherein the pellet contains a stoichiometric amount of materials represented by the formula Li[Nio.83Mno.o6Coo.ii]o.9975Zro.oo2502.

[0036] In some aspects, the techniques described herein relate to a pelletized cathode formulation, wherein the pellet contains a stoichiometric amount of materials represented by the formula Lii+x[(NinCocAlm)i-aAa]i-xO2 where: A is selected from the group consisting of Mg, Si, Ca, Ti, V, Zn, Sr, Zr, Nb, Mo, Sn, Sb, Ba, and combinations thereof; - 0.05 < x < 0.10; n + m + c = 1; and 0 < a < 0.05.

[0037] In some aspects, the techniques described herein relate to a pelletized cathode formulation, wherein the pellet contains a stoichiometric amount of materials represented by the formula LixMm-y-zNiyMzOi where: M is selected from the group consisting of Mg, Al, Si, Ca, Ti, V, Co, Zn, Sr, Zr, Nb, Mo, Sn, Sb, Ba, and combinations thereof; 0.25 < x < 1.1; 0.3 < y < 0.5; and 0 < z < 0.15.

[0038] In some aspects, the techniques described herein relate to a pelletized cathode formulation, wherein the pelletized cathode formulation is configured for the production of a cathode material having a cubic spinel structure with single cry stalline morphologies.

[0039] In some aspects, the techniques described herein relate to a pelletized cathode formulation, wherein the pelletized cathode formulation consists essentially of a cathode material having a having a single crystalline rock salt structure.BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Features of examples of the present disclosure will become apparent by reference to the following detailed description and drawings, in which like reference numerals correspond to similar, though perhaps not identical, components. In addition to the features described herein, additional features and variations will be readily apparent from the following descriptions of the drawings and exemplary embodiments. It is to be understood that these drawings depict various embodiments and are not intended to be limiting in scope.

[0041] Figure 1 shows photographs of (a) non-pelletized and (b) pelletized precursor mixture of SI and S2 materials of Example 1.

[0042] Figure 2 shows SEM images of SI and S2 materials of Example 1.

[0043] Figure 3 shows the XRD patterns of (a) SI and (b) S2 materials of Example1.

[0044] Figure 4 shows the first cycle charge-discharge profiles at C / 20 of coin-cells made with (a) S I and (b) S2 materials.

[0045] Figure 5 shows the (a) discharge capacity and (b) capacity retention at C / 5 of coin-cells made with S 1 and S2 materials.

[0046] Figure 6 shows SEM images of S3, S4, S5, and S6 materials of Example 2.

[0047] Figure 7 shows the (a) cation mixing and (b) lithium residues of S3, S4, S5, and S6 materials of Example 2.

[0048] Figure 8 shows the (a) discharge capacity and (b) capacity retention at C / 5 of coin-cells made with S3, S4, S5, and S6 materials.

[0049] Figure 9 shows SEM images of S7 and S8 materials before deagglomeration of Example 3.

[0050] Figure 10 shows SEM images of S7 and S8 materials after deagglomeration of Example 3.

[0051] Figure 11 shows the XRD patterns of (a) S7 and (b) S8 materials of Example 3.

[0052] Figure 12 shows the (a) discharge capacity and (b) capacity retention at C / 5 of coin-cells made with S7 and S8 materials.

[0053] Figure 13 shows the XRD patterns of (a) S 10, (b) S 11 and (c) S 12 materials of Example 4.

[0054] Figure 14 illustrates a flow chart including pelletization of precursors to synthesize lithium transition metal oxide materials.

[0055] Figure 15 illustrates an additional flow chart including pelletization of lithium transition metal oxide materials.DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0056] The foregoing and other aspects of the present disclosure will now be described in more detail with respect to the description and methodologies provided herein. This description is not intended to be a detailed catalogue of all the ways in which the embodiments of the present disclosure may be implemented, or of all the features that may beadded to the present disclosure. For example, features illustrated with respect to one embodiment may be incorporated into other embodiments, and features illustrated with respect to a particular embodiment may be deleted from that embodiment. In addition, numerous variations and additions to the various embodiments suggested herein, which do not depart from the instant disclosure, will be apparent to those skilled in the art in light of the instant detailed description, figures and claims. Hence, the following specification is intended to illustrate some particular embodiments, and not to exhaustively specify all permutations, combinations, and variations thereof.

[0057] In the following detailed description, reference is made to the accompanying drawings, which form a part hereof. In the drawings, similar symbols typically identify similar components, unless context dictates otherwise. The illustrative embodiments described in the detailed description, drawings, and claims are not meant to be limiting. Other embodiments may be utilized, and other changes may be made, without departing from the spirit or scope of the subject matter presented herein. It will be readily understood that the aspects of the present disclosure, as generally described herein, and illustrated in the figures, can be arranged, substituted, combined, separated, and designed in a wide variety of different configurations, all of which are explicitly contemplated herein.

[0058] The methods disclosed herein provide advantages over previous methods. Large-scale all-dry synthesis of cathode materials presents several challenges. Unlike the traditional co-precipitation method, which involves the use of excessive amounts of liquid or water, an all-dry synthesis of cathode materials relies on physically or mechanically mixing transition metal feedstocks, Li source, and dopants in a liquid-free environment followed by sintering. The all-dry process is particularly suitable for synthesizing single cry stal cathode materials, as the mixed precursors undergo high temperature sintering to ensure a uniform and homogeneous transition metal distribution. However, the sintered materials may form large agglomerates with varying particle sizes and residual compounds may be present. This may happen primarily because the mixed precursors are not single phase and not as uniform as the transition metal hydroxide precursor made from the wet co-precipitation counterparts. An alldry mixed precursor having distinct pores distributed along individual boundaries may suffer from non-uniform grain growth during high-temperature sintering. Consequently, the final product obtained may be non-uniform, both in particle size and elemental distribution. This issue may become even more severe when dopants are present, as their distribution can significantly alter the physical and chemical properties of the synthesized cathode materials.This is a large gap that needs to be filled between lab-scale achievement and commercialization, and this gap is addressed by embodiments of the methods described herein.

[0059] The production of single crystal positive electrode materials can be achieved through the all-dry synthesis process disclosed herein. The inventors have previously conducted trials where transition metal feedstocks, Li sources, and dopants are thoroughly mixed followed by high-temperature firing. However, achieving atomic-scale mixing homogeneity and uniform elemental distribution in the final products remains a significant challenge at scale. This is due to the non-uniform phase, grain boundary mismatch, particle size difference, and other properties when multiple feedstocks are mixed. When producing a large scale dry-mixed precursor in a porous substrate, lithiation kinetics may be enhanced due to increasing the heating rate, oxygen flow, and temperature. However, the presence of void spaces between individual feedstocks, lithium source, and dopants hinder transition metal interdiffusion during the sintering process, resulting in a non-uniform product, both in morphology and transition metal distribution. This issue becomes significantly challenging in the presence of dopants. In certain circumstances, gases generated from the lithiation reaction, such as CO2 and H2O, may react with the sintered materials, especially those with high-Ni, resulting in high lithium impurities. These lithium impurities have a detrimental effect on slurry preparation while applying the cathode materials to a current collector and cell performance.

[0060] Embodiments of methods disclosed herein advantageously solve the problems faced by the inventors. For example, pelletization techniques described herein can be applied to the precursor mixture to increase lithiation kinetics and transition metal diffusion by reducing interstitial gaps between feedstocks, increasing grain boundaries, and reducing contact area with a reactive substrate, such as a highly reactive saggar, during firing. The methods described herein can also enhance gas diffusion and contact area when elemental metal is utilized as a feedstock or when a specific sintering environment is required. The enhancement of gas diffusion during sintering is generally beneficial for the oxidization of elemental metals that are in their reduced state, such as elemental nickel, manganese, or cobalt. The compression and pelletization of materials may be somewhat counterintuitive considering the reduction in porosity for the diffusion of gases. However, the inventors have discovered that compression and pelletization of the cathode precursor mixtures both reduces lithium residuals and enhances gas diffusion during sintering. In some embodiments the gas diffusion may be further enhanced through the use of a porous substrate, such as a porous ceramic saggar substrate or a porous ceramic layer.

[0061] Aspects of this disclosure presented herein relate to pelletization processes for the sintering of all-dry synthesis positive electrode material. For example, some embodiments relate to pelletization methods for sintering of all dry synthesis of lithium transition metal oxide positive electrode materials. Pelletization of cathode powder can, in some embodiments, increase lithiation kinetics and improve homogeneity for cathode material manufacture, for example in embodiments which involve materials that require the use of specific sintering conditions, such as high-Ni, Co-free, or high-Mn materials. Some embodiments of methods disclosed herein also enable the use of a porous saggar in manufacturing-scale synthesis. In some embodiments, the methods described in this disclosure result in single-cry stalline materials having high crystallinity, homogeneity, and excellent electrochemical performances.

[0062] Figure 14 depicts a general process for some embodiments herein. The figure is a flowchart of an example method for the pelletization of precursors to synthesize lithium transition metal oxide materials. At step 1410, the method comprises preparing a precursor mixture by mixing a stoichiometric amount of one or more transition metal feedstocks, one or more lithium sources, and one or more optional dopants in a liquid-free environment. At step 1420, the method comprises pelletizing the precursor mixture into one or more pellets. At step 1430, the method comprises heating the pelletized precursor mixture on porous layer to produce lithium transitional metal oxide positive electrode material. The porous layer may be a ceramic layer or substrate with one or more layers having different porosities.

[0063] The process depicted in Figure 14 is a dry process or is substantially free of solvents and solvent residue. Specifically, the process from step 1410 to step 1430 is a dry process that is free of solvents, which may be liquid at room temperature.

[0064] The heating in step 1430 may be performed in an oxygen atmosphere, an oxygen-rich atmosphere, a reduced carbon dioxide atmosphere, and / or in an atmosphere having dry air. Oxygen containing atmospheres used heating procedures should be selected such that the oxygen partial pressure is sufficient for the positive electrode material to form and so that oxygen is the only element from the oxygen containing atmosphere that is substantially incorporated in the precursor mixture. Examples of oxygen containing atmospheres suitable for the feedstock mixture heating procedure include 02(g), air, or mixtures of oxygen with other gases, including inert gases such as Nz(g), Ar(g), and other oxygen containing gases, such as CO2

[0065] The precursor mixture may be any mixture for producing battery cathode materials. Advantageously the process may be used to pelletize and sinter battery cathodematerials having one or more dopants. In some embodiments the stoichiometry of the precursor mixture may be represented by the general formula LxTvMzCh where x > 0.2, y > 0.5, and 0.2 > z > 0.001; L consists of one or more insertable alkali metals (in the case of Li-ion batteries L is lithium); T consists of one or more first row transition metal elements; and M consists of one or more metal elements other than an alkali metal or a first-row transition metal element. In some embodiments, x is about 1, y + z is about 1. and z is less than about 0.1. In some embodiments, x is 1. y + z is 1, and z is less than 0.1. In some embodiments M consists of one or more metal elements other than iron, alkali metals, and first-row transition metal elements. In some embodiments T is three or more first row transition elements. In some embodiments T is Ni, Mn, and Co and each of their molar amounts add up to y. Advantageously, the stoichiometry of the precursor mixture represented by the general formula LxTyMzCh is free of solvents or solvent residues. T and M may have the same composition or substantially the same composition as the battery cathode material produced after firing, but L may be provided in the precursor mixture in 10% excess.

[0066] The stoichiometry of the precursor mixture for pelletization may also be represented by the general formula Lii+x[(NinMnmCoc)i-aAa]i-xO2, where -0.03 < x < 0.06; n + m + c = 1; n > 0.05; m > 0.05; c > 0.05; A is a metal dopant; and 0 < a < 0.05. Where a dopant is present, the precursor mixture may have 0.0001 < a < 0.05. In addition to the precursor mixture, the pellet or sintered pellet may be represented by this general formula. Advantageously, the composition represented by the general formula Lii-x[(NinMnmCoc)i- aAa]i-xO2 is free of solvents or solvent residues. The dopant may be selected from the group consisting of Na, B, Al, Mg, Zr, Nb, Fe, Si, P, Mo, Ba, Sr, Ca, Zn, Cr, V, W, Nd, La, Cs, Ta, Ce, Cu, Eu, Ti. Sn, Sb, Pb, Bi, Rb, and mixtures thereof. In some embodiments the dopant is Zr and 0.001 < a < 0.02. In some embodiments the composition may be a stoichiometric ratio to create NMC622 or NMC83 with lithium in at least 1% excess.

[0067] In some embodiments the stoichiometry of the precursor mixture has the general formula of LixMn2-y-zNiyMzO4 where: M is selected from Mg, Al, Si, Ca, Ti, V, Co, Zn, Sr, Zr, Nb, Mo, Sn, Sb, Ba, and a combination thereof; 0.25 < x < 1. 1; 0.3 < y < 0.5; and 0 < z < 0. 15. In some embodiments 0 < z < 0. 15. The cathode materials represented by the general chemical formula of LixMm-y-zNiyMzCh may be lithium manganese oxide battery cathode materials (LMO). The particle size of the LMO battery materials may have a D50 particle size in the range of about 1 pm to about 30 pm, about 10 pm to about 30 pm, about 1 pm to about 20 pm. about 1 pm to about 10 pm, about 0.5 pm to about 30 pm or any range of values in between.

[0068] In some embodiments the stoichiometry of the precursor mixture has the general chemical formula of Lii+x[(NinCocAlm)i-aAa]i-x02 where: A is selected from Mg. Si, Ca, Ti, V, Zn, Sr, Zr, Nb, Mo, Sn, Sb, Ba, and a combination thereof; -0.05 < x < 0.10; n + m + c = 1; and 0 < a < 0.05. In some embodiments n is greater than zero, c is greater than zero, and m is greater than zero. The cathode materials represented by the general chemical formula of Lii+x[(NinCocAlm)i-aAa]i-xO2 may be lithium nickel cobalt aluminum battery cathode materials (NCA).

[0069] In some embodiments the stoichiometry of the precursor mixture has the general chemical formula AxTyMzPO4 in which x, y and z are numbers with x > 0, y > 0.5, and z> 0; y + z = l; A is one or more insertable alkali metals; T is one or more first row transitional metals; and M is a dopant that consists of one or more metal elements that are not an alkali metal or a first-row transition metal. In some embodiments, x, y, and z are numbers with 1.2 > x > 0.9, 1 > y > 0.9, and 0. 1 > z > 0. In the case of Li-ion batteries, A is lithium. T may consist of one or more first-row transition metals, x is equal to about 1, y is about 1, and z < 0.1. In some embodiments, T is Fe. In some embodiments, T includes Mn and Fe. In some embodiments, M consists of one or more of Mg, Al, Ti. Zr. W. Zn. Mo, K. Na. Si. Nb. and Ta when z is greater than 0.

[0070] In some embodiments, the precursor mixture is comprised of a mixture of elements to produce lithium manganese phosphate (LMP) or lithium manganese iron phosphate (LMFP). In some embodiments the precursor mixture may contain iron and contain a stoichiometric ratio to produce lithium iron phosphate cathode materials (LiFePCh or ‘"LFP”). However, in other embodiments the precursor mixture may be free of iron.

[0071] In some embodiments the precursor mixture is comprised of a mixture of elements to produce a single crystalline rock salt phase structure or a single crystalline cubic spinel structure. In some embodiments the cubic spinel crystalline structure is ahigh-Mn spinel structure. In some embodiments the Mn rich spinel is cobalt free LNMO and may have the formula LiNio.5Mn1.5O4.

[0072] In some embodiments the precursor mixture is comprised of a mixture of elements to produce a lithium rich cathode material or lithium rich manganese (LMR) cathode material. In some embodiments the lithium rich material has the general formula xLi2MnO3-(l - x)LiMO2 where M = Mn, Ni, Co, Fe, etc.. In embodiments where M=Mn the lithium rich cathode material may be comprised of a combination of trigonal L1MO2 and monoclinic Li2MnO?. Advantageously, the lithium rich battery materials may be optimized to have a specific capacity in the range of 220 mAh*g1to 240 mAh*g1or even >240 mAh*g1.

[0073] In some embodiments the precursor mixture may be a mixture having a stoichiometric ratio for a single cry s tall ine sodium cathode material. A person having ordinary skill in the art would appreciate that various different kinds of cathode materials may benefit from mechanical compression prior to heating or sintering.

[0074] The precursor mixture may have the same composition or substantially the same composition as the battery cathode material produced after firing. In some embodiments the precursor mixture may have the same composition as the NMC, LFP, LMNO. NCA, LMO. or LCO battery cathode material produced after firing but lithium may be provided in excess prior to the firing. In some embodiments the precursor mixture may have the substantially the same composition as the nickel, manganese, and cobalt in the resulting battery cathode material, but have a different composition with regard to lithium and the dopant (A).

[0075] Figure 15 depicts a pelletization and coating process for some embodiments herein. The figure is a flowchart of an example method for preparing a coated lithium transition metal oxide electrode material for a battery'.

[0076] At step 1510, the method comprises preparing a precursor mixture by mixing a stoichiometric amount of one or more transition metal feedstocks, one or more lithium sources, and one or more optional dopants in a solvent-free environment. At step 1520, the method comprises pelletizing the precursor mixture into one or more pellets. At step 1530, the method comprises heating the one or more pellets on a substrate or on one or more partially porous substrates or layers to produce a heated pellet. At step 1540, the method comprises pulverizing the heated pellet through milling or grinding to produce a pulverized material. At step 1550, the method comprises mixing the pulverized material with one or more coating materials or one or more additional lithium sources to produce a coated material. At step 1560, the method comprises repelletizing the powder mixture to produce a repelletized material. At step 1570, the method comprises reheating the repelletized material to produce a coated lithium transition metal oxide cathode material.

[0077] Advantageously, the process in Figure 15 is an all-dr ' process that is free of solvents or solvent residues. For example, the process from step 1510 to step 1570 is free or substantially free of solvents. The process illustrated in Figure 15 may also be free of iron or iron compounds. In some embodiments the pelletization pressure may be larger in step 1520 and lower in step 1560 for repelletization. In some embodiments the pelletization pressure may be lower in step 1520 and higher in step 1560 for repelletization. In some embodiments the first pelletization pressure may differ by at least 10% from the repelletization pressure.

[0078] The coated lithium transition metal oxide cathode material of step 1570 may be represented by the general formula Lii+x[(NinMnmCoc)i-aAa]i-xO2, where -0.03 < x < 0.06; n + m + c = 1; n > 0.05; m > 0.05; c > 0.05; A is a metal dopant; and 0.0001 < a < 0.05. The dopant may be selected from the group consisting of Na, B, Al, Mg, Zr, Nb, Fe, Si, P, Mo, Ba, Sr, Ca, Zn, Cr, V, W, Nd, La, Cs, Ta, Ce, Cu, Eu, Ti, Sn, Sb, Pb, Bi, Rb, and mixtures thereof. In some embodiments the dopant is Zr and 0.001 < a < 0.02. In some embodiments the dopant is at least partially applied in 1560 as a coating material. In some embodiments the heated pellet in step 1530 and the coated lithium transition metal oxide cathode material in step 1570 have an 03 layered structure.

[0079] In embodiments, the process is an all-dry process from the mixture of the feedstock materials to the time that the sintered cathode material or coated cathode material is applied onto a cunent collector. The deposition of the cathode material on a current collector may be facilitated by a solvent or it may be performed in a dry or substantially dry manner. The disclosed process is superior to that of the prior art, as the pellet or pelletized material does not have contamination that can result from solvent residues or additional steps requiring the evaporation of solvents. For example, the process of the present disclosure removes various washing or solvent purification steps that can add cost or complexity to the production of high- quality7cathode materials.

[0080] The processes disclosed herein were verified via trials having pelletized and non-pelletized compositions. For example, Figure 1 shows the photographs of positive electrode materials after sintering in a saggar with (a) non-pelletized- and (b) pelletized- precursor mixture. Although a ceramic saggar is demonstrated in Figure 1, a person of ordinary skill in the art would understand that other porous substrates may be used, such as a porous ceramic layer comprises of ceramic materials. One such layer may be a porous ceramic layer comprised of separate ceramic components. It will be appreciated that the porous substrate or layer should be selected based upon the substrate or layer’s ability to withstand high sintering temperatures in excess of 700 degrees Celsius. Other materials may be envisioned such as porous glass or composite materials. A ceramic material is particularly advantageous as ceramics are generally temperature resilient. For example, although a dish-shaped ceramic substrate is depicted, a flat or substantially flat substrate or a layer with substantially constant thickness may be provided, because the pelletized material generally retains its vertical and horizontal pelletized form during sintering.

[0081] The pellets made from the precursor mixture may be spaced on a substrate to increase airflow during sintering. For example, the pellets may be separated by at least halfof the distances of their largest width. Where the pellets are substantially conical or frusto conical, the pellets may be separated by at least half of the largest diameter. The pellet may also be in the shape of a cylinder, sphere, pyramid, prism, cuboid, or cube. The compressed portion of the pellet is free of excess internal voids that are larger than 0.5 cm, as excess voids can reduce reaction kinetics during sintering. As discussed above, decreasing air voids in the pelletized materials can counterintuitively increase diffusion of gases during sintering.

[0082] The size of the pellets may be reduced or optimized in order to increase the total surface area of the pelletized precursor material, which increases the potential for oxygen diffusion. For example, the cylindrical pellets may have a diameter of about 5.08 cm (2 inches) and a height of about 5.08 cm (2 inches).

[0083] The procedures disclosed herein show improved chemical performance due, in part, to reduced cation mixing or cation disorder where larger cations such as Ni, Co, or Mn are located where Lithium ions are intended to be or within Lithium layers. Cation mixing can cause reduced electrochemical performance for several reasons. For example, it can disrupt the ordered structure of cathode materials and affect the ability of the cathode material to store and release lithium ions, which reduces the overall efficiency of the cathode material.

[0084] Cation disorder can also increase the internal impedance of the cathode material, making it less conductive. This increases the resistance for ion diffusion and electron transport, which can lead to reduced battery performance. Further, since the ordered structure of the cathode material is disrupted, such as the order of a crystalline material, the structural stability of the material decreases to an extent. This can bring about structural distortions in a crystalline material, where disproportionately sized cations weaken the lattice. Materials with low cation mixing can be less prone to phase transformation and cracking during cycling. Thus, the disclosed process is desirable at least because it prevents disorder in cation arrangements in single crystal cathode materials. In some embodiments the percent of cation mixing is less than about 7% or the amount of Ni, Co, or Mn in the Li layers is less than about 7%.

[0085] The processes in embodiments herein are also advantageous at least in part because they reduce lithium residuals on the surface of the cathode materials. Lithium residuals generally comprise unreacted byproducts of lithium precursor materials, such as LiOH, Li2O. and Li2CC>3. These residuals on the surface of the cathode materials are undesirable because they can lead to side reactions that reduce battery capacity. The oxidation of these compounds may result in the formation of Li2O and CCh gas at higher voltages, which lowers the coulombic efficiency between the charge and discharge capacities during cycling. The creation of gases can also cause fracture or failure of the battery or battery active materials. Finally,lithium impurities can also have a detrimental effect on slurry preparation, when applying cathode materials to a current collector, and the creation of the cathode itself.

[0086] In embodiments disclosed herein are methods of preparing a lithium transition metal oxide positive electrode material. In some embodiments, the lithium transition metal oxide positive electrode material may be used in a battery. In some embodiments, the battery is a secondary battery, for example a battery which can be charged and discharged multiple times. In some embodiments, the method is an all-dry method.

[0087] In some embodiments, the lithium transition metal oxide positive electrode material is a Lii+x[(NinMnmCoc)i-aAa]i-xO2, where -0.03 < x < 0.06; n + m + c = l; n > 0.05; m > 0.05; c > 0.05; A is a metal dopant; and 0 < a < 0.05 electrode material. In some embodiments a dopant is present and 0.0001 < a < 0.05. Accordingly, in some embodiments, disclosed herein are methods for preparing a Lii+x[(NinMnmCoc)i-aAa]i-xO2, where -0.03 < x < 0.06; n + m + c = 1; n > 0.05; m > 0.05; c > 0.05; A is a metal dopant; and 0.0001 < a < 0.05 electrode material for a battery7.

[0088] In some embodiments, the method includes preparing a precursor mixture by mixing a stoichiometric amount of one or more transition metal feedstocks, one or more lithium sources, and one or more dopants in a liquid-free environment. For example, the environment may be free or substantially free of liquids.

[0089] In some embodiments, the one or more transition metal feedstocks and the one or more dopants are selected from the group consisting of: elemental metal, oxides, hydroxides, oxyhydroxides, carbonates, sulfates, nitrates, acetates, and combinations thereof. In some embodiments, the one or more transition metal feedstocks comprise nickel, manganese, and cobalt metal feedstocks. Accordingly, in some embodiments, the method includes preparing a precursor mixture by mixing a stoichiometric amount of nickel, manganese, and cobalt metal feedstocks, one or more lithium sources, and one or more dopants in a liquid-free environment.

[0090] In some embodiments, the one or more lithium sources are selected from the group consisting of: Li carbonate, Li oxide. Li hydroxide, Li hydroxide monohydrate, Li acetate. Li chloride, Li fluoride, Li nitrate. Li sulfate, and mixtures thereof.

[0091] In some embodiments, the one or more dopants is selected from the group consisting of: Na, B, Al, Mg, Zr, Nb, Fe, Si, P, Mo, Ba, Sr, Ca, Zn, Cr, V, W, Nd, La, Cs, Ta, Ce, Cu, Eu, Ti, Sn, Sb, Pb, Bi, Rb, and mixtures thereof. In some embodiments, the one or more dopants include Zr. In some embodiments, the one or more dopants are configured to limit transition metal interdiffusion. The dopants may be selected to reduce voids in thepelletized material in order to prevent unwanted lithium impurities and the creation of gases. In some embodiments the dopant is selected from Na, B, Al, Mg, Zr, Nb, Fe, Si, P, Mo. Ba. Sr, Ca, Zn, Cr, V, W, Nd, La, Cs, Ta, Ce, Cu, Eu, Ti, Sn, Sb, Pb, Bi, Rb. In some embodiments the dopant may be in elemental form, I, II, or III oxidization state, or in the form of oxides, hydroxides, oxy hydroxi des, carbonates, sulfates, nitrates, acetates. In some embodiments the dopant is a zirconium dopant. In some embodiments the dopant is a Zr(OH)4 powder. The dopant may be provided in a stoichiometric ratio in order to prevent excess voids from forming in the pelletized material.

[0092] In some embodiments, the method further includes pelletizing the precursor mixture into one or more pellets. Pelletizing may be performed by any method known to those of skill in the art. In some embodiments, pelletizing the precursor mixture includes mechanically compressing the precursor mixture into one or more pellets. In some embodiments, the precursor mixture is pelletized using a hydraulic press. In some embodiments, pelletization of precursor mixture with the hydraulic press comprises the use of a pellet press die set, pelletizer, extruder, hot melt extrusion, melt agglomeration, spheronization. cryopelletization, or a combination thereof.

[0093] In some embodiments, the pressure applied to the pelletized mixture through hydraulic press is in a range of about 0. 1 MPa to about 100 MPa, for example about 0.1 MPa, about 1 MPa, about 2 MPa, about 3 MPa, about 4 MPa, about 5 MPa. about 6 MPa, about 7 MPa. about 8 MPa, about 9 MPa, about 10 MPa, about 11 MPa. about 12 MPa. about 13 MPa, about 14 MPa, about 15 MPa, about 16 MPa, about 17 MPa, about 18 MPa, about 19 MPa, about 20 MPa, about 21 MPa, about 22 MPa, about 23 MPa, about 24 MPa, about 25 MPa, about 26 MPa, about 27 MPa. about 28 MPa, about 29 MPa, about 30 MPa, about 31 MPa, about 32 MPa. about 33 MPa, about 34 MPa, about 35 MPa, about 36 MPa, about 37 MPa, about 38 MPa, about 39 MPa, about 40 MPa, about 45 MPa, about 50 MPa, about 55 MPa, about 60 MPa, about 65 MPa, about 70 MPa, about 75 MPa, about 76 MPa, about 77 MPa, about 78 MPa, about 79 MPa, about 80 MPa, about 85 MPa, about 86 MPa, about 87 MPa, about 88 MPa, about 89 MPa, about 90 MPa, about 95 MPa, about 100 MPa, or a range constructed from any of the aforementioned values including about 2 MPa to about 30 MPa. about 4 MPa to about 20 MPa, at least about 2 MPa, at least about 4 MPa, or at least about 6 MPa. Advantageously pressures greater than about 0.1 MPa reduces lithium residuals and improves the charge and discharge characteristics of the cathode material. Pressures below about 100 MPa can reduce voids in the pelletized material while still allowing oxygen diffusion.

[0094] In some embodiments, the pellet is in the shape of a cylinder, sphere, cone, pyramid, prism, cuboid, cube, or a combination thereof.

[0095] In some embodiments, the pellet prior to sintering has a porosity of about 5% to about 90 %, for example about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about66%, about 67%. about 68%. about 69%, about 70%, about 71%, about 72%, about 73%, about74%. about 75%. about 76%. about 77%, about 78%, about 79%, about 80%, about 81%, about82%, about 83%, about 84%, about 85%, about 86%, about 87%, about 88%, about 89%, about90%, or a range constructed from any of the aforementioned values. In some embodiments the porosity of the pellet is less than about 90%, less than about 80%. less than about 70%, less than about 60%, less than about 50%, less than about 40%, less than about 30%. less than about 20%, or any range of values between (i.e. about 40% to about 90%). In some embodiments the pellet has a porosity less than about 70% prior to heating.

[0096] Sintering or heating at temperatures in excess of about 300°C can greatly reduce the porosity of the pellets, such that the pellets have little or no porosity. In some embodiments the pellet has a porosity less than about 20% after heating, less than about 10% after heating, less than about 5% after heating, less than about 2% after heating, less than about 0.1% after heating, or any range of values in between (i.e. between 0% and 2% porosity').

[0097] In some embodiments, the method further includes heating the pelletized precursor mixture on a porous substrate or layer. In some embodiments, the porous substrate comprises a porous ceramic saggar.. In some embodiments, the method further includes heating the pelletized precursor mixture on a porous ceramic saggar to produce a lithium transitional metal oxide positive electrode material.

[0098] In some embodiments, the ceramic saggar or ceramic material has an apparent porosity ranging from about 0% to about 50%, for example about 0.1%, about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%. about 20%. about 21%, about 22%, about 23%, about 24%, about 25%, about 26%. about 27%. about 28%. about 29%, about 30%, about 31%, about 32%, about 33%, about 34%, about 35%, about 36%, about 37%, about 38%, about 39%, about 40%, about 41%, about 42%, about 43%, about 44%, about 45%, about 46%, about 47%, about 48%, about 49%, about 50%, or a range constructed from any of the aforementioned values. In some embodiments the ceramic saggar has an apparent porosity less than 50%, less than 40%, less than 30%. less than 20%, less than 10%, or any range of values between.

[0099] In some embodiments, heating the pelletized precursor mixture is carried out under an atmosphere of inert gas, oxygen, a reduced oxygen partial pressure gas, dry air, or air.

[0100] In some embodiments, the heating temperature is in a range between about 450 °C to about 1200 °C, and may include temperatures of about 450 °C, about 500 °C, about 550 °C, about 600 °C, about 650 °C. about 700 °C, about 750 °C, about 800 °C, about 850 °C, about 900 °C, about 950 °C. about 1000 °C. about 1 100 °C or a range constructed from any of the aforementioned values. In some embodiments, heating is carried out with one or more temperature holds. For example, the pelletized precursor mixture may be gradually heated to increasing temperatures, with one or more temperature holds at one or more pre-determined temperatures.

[0101] In some embodiments, the method additionally comprises pulverizing the heated, pelletized precursor mixture to produce pulverized material. Pulverizing may be accomplished by any method known in the art, for example, through at least one of impact milling, jet milling, or grinding. For example, the method may include a step of impact milling, jet milling, or grinding the precursor mixture after it has been pelletized and heated.

[0102] In some embodiments, the method further comprises mixing the pulverized material with one or more coating materials and / or one or more additional lithium sources to produce coated material. In some embodiments, the one or more coating materials may comprise of Li, Na, Mg. Ba, Ti. Zr. Nb, Ta, Mo. W. Mn, Co, Zn, B, Al, C. Si. Sn. P, Bi. In some embodiments the coating materials may be in elemental form, I, II, or III oxidization state, or in the form of oxides, hydroxides, oxyhydroxides, carbonates, sulfates, nitrates, acetates. In some embodiments, the one or more additional lithium sources is selected from selected from the group consisting of: Li carbonate, Li oxide, Li hydroxide, Li hydroxide monohydrate, Li acetate, Li chloride, Li fluoride, Li nitrate, Li sulfate, and mixtures thereof, and may be the same or different from the first lithium source. Mixing with the coating materials may be performed by any method known to those of skill in the art.

[0103] In some embodiments, the method further comprises repelletizing the coated material to produce repelletized material. Repelletization may be performed by any of the methods described above with respect to pelletization, for example by hydraulic press with pressures in the range of 0.1 to 100 MPa.

[0104] In some embodiments, the method further comprises reheating the repelletized material. Reheating may be performed by any of the methods described above with respect to heating the pelletized precursor mixture. For example, the reheating temperature maybe in a range betw een about 450 °C to about 1100 °C, and may include one or more temperature holds.Li-ion Batteries

[0105] The methods disclosed herein relate to Li-ion batteries. In some embodiments, the Li-ion battery is a secondary battery. In some embodiments, the Li-ion battery comprises a cathode material, an anode material, one or more cunent collectors, one or more separators, and one or more electrolytes.

[0106] In some embodiments, the Li-ion battery' comprises a positive electrode material. In some embodiments, the positive electrode material comprises a lithium transition metal oxide material as further described above. For example, the lithium transition metal oxide material may be produced from any of the methods described above.

[0107] In some aspects, the disclosure relates to a battery containing the lithium transition metal oxide material produced according to embodiments disclosed herein. The battery materials disclosed herein may be incorporated into various consumer or commercial devices. Examples include but are not limited to personal electronic devices, electric cars or mobility devices, battery' energy storage devices, electric tools, electric bicycles, electric toys, or any other electrically powered device. The lithium transitional metal cathode materials produced herein may be coated onto a current collector with one or more binders or conductive additives.Definitions

[0108] Although the following terms are believed to be well understood by one of skill in the art, the following definitions are set forth to facilitate understanding of the presently disclosed subject matter.

[0109] All technical and scientific terms used herein, unless otherwise defined below', are intended to have a meaning w ould be understood by one of ordinary skill in the art. References to techniques employed herein are intended to refer to the techniques as commonly understood in the art, including variations on those techniques or substitutions of equivalent techniques that would be apparent to one of skill in the art.

[0110] As used herein, the terms “a” or “an” or “the” may refer to one or more than one. For example, “a” dopant can mean one dopant or a plurality of dopants.[OHl] As used herein, the term "and / or" refers to and encompasses any and all possible combinations of one or more of the associated listed items, as well as the lack of combinations when interpreted in the alternative (“or”).

[0112] The term “cathode” should be given its ordinary meaning as it would be understood by a person having ordinary skill in the art at the time of the disclosure but often refers to the electrode at which reduction occurs when a metal-ion is discharged. In a lithium ion cell, the cathode is the electrode that is lithiated during discharge and dehthiated during charging.

[0113] The term “heating” as used herein should be interpreted as would be understood by a person having skill in the art but also refers to may refer to heating with or without calcination. In some embodiments herein, heating refers to heating at a temperature in excess of 450 degrees Celsius.

[0114] The term “dopant” should be given its ordinary meaning as it would be understood by a person having ordinary skill in the art at the time of the disclosure but often refers to metals capable of serving as a dopant in a lithium transition metal oxide. In some instances “dopant” includes the metals Na, B, AL Mg, Zr, Nb. Fe. Si, P. Mo, Ba, Sr, Ca, Zn. Cr, V, W, Nd, La, Cs, Ta, Ce, Cu, Eu, Ti, Sn, Sb, Pb, Bi, Rb, and mixtures thereof but excludes the metals Ni, Mn, and Co. In some instances, “dopant” includes transition metals in elemental form, transition metal compounds, or non-transition metal compounds but excludes Ni, Mn, and Co.

[0115] The term “stochiometric amount” should be given its ordinary meaning as it would be understood by a person having ordinary skill in the art at the time of the disclosure but also refers to an amount of reactants in a chemical reaction that allow s the reactants to react completely, based on the mole ratios indicated by the balanced chemical equation.

[0116] The term “liquid-free environment” should be given its ordinary meaning as it w ould be understood by a person having ordinary skill in the art at the time of the disclosure but generally refers to an environment that is free or substantially free of solvents including organic or aqueous solvents that are liquids around room temperature. A “liquid-free environment” generally excludes solvents in liquid form but does not exclude solid hydrates, such as the solid hydrate LiOH-FLO.

[0117] The term “lithium residues” should be given its ordinary' meaning as it would be understood by a person having ordinary skill in the art but generally refers to the unreacted byproducts of lithium precursor materials, such as LiOH, Li2O, and Li2CO3, which remain on the surface of a cathode material. Lithium residues are generally undesirable becausethey can lead to unwanted side reactions that reduce battery capacity. The oxidation of these compounds may result in the formation of Li2O and CO2 gas at higher voltages, which lowers the coulombic efficiency between the charge and discharge capacities during cycling. Lithium residues can also be called lithium residuals.

[0118] The term “half-cell” should be given its ordinary meaning as it would be understood by a person having ordinary skill in the art at the time of the invention but often refers to a cell that has a working electrode and a metal counter / reference electrode. A lithium half-cell has a working electrode and a lithium metal counter / reference electrode.

[0119] The term “substantially free” should be given its ordinary' meaning as it would be understood by a person having ordinary' skill in the art at the time of the invention but often refers to a minimal amount of something in a material. For example, in some embodiments substantially free means a material may contain less than 1% of something that it is “substantially free” of, preferably less than 0.1%.

[0120] The term “free of' should be given its ordinary' meaning as it would be understood by a person having ordinary skill in the art at the time of the invention but often refers to an insignificant or de minimis amount of something. In certain embodiments herein, the material may only contain trace amounts of the substance (such as water or a solvent) that it is “free of.”

[0121] “Impact milling” should be given its ordinary meaning as it would be understood by a person having ordinary skill in the art at the time of the invention but generally refers to the process of particle pulverization due to particle impact with other particles, with milling apparatus or with milling media. Impact milling may be conducted with the particles in a gas or vacuum (dry impact milling), where gases such as air or inert gases, including nitrogen may be used. Dry impact milling methods are generally preferred over wet impact milling methods, since dry impact milling methods avoid additional steps, such as filtering or drying, associated with utilizing wet impact milling methods. Some impact milling methods may include jet milling, pin milling, and centrifugal impact milling. In some aspects the milling is impact milling with a coffee grinder or other commercial apparatus that simulates the milling forces thereof.

[0122] The term “single crystal morphology” should be given its ordinary meaning as it would be understood by a person having ordinary skill in the art at the time of the invention but generally refers to refers to a crystalline solid where the particle consists essentially of a single crystal and may also be referred to as a “monocrystal”. A single crystal morphology is essentially free from interparticle boundaries.

[0123] The term “secondary particle’' is intended to refer to a particle produced after the sintering of a stoichiometric amount of feedstock materials including feedstock metals, lithium sources, and / or dopants.

[0124] The term “dry air” should be given its ordinary meaning as it would be understood by a person having ordinary7skill in the art at the time of the invention but generally refers to air with a relative humidity less than about 10%.

[0125] The term “metal-ion cell” or “metal-ion battery” should be given its ordinary meaning as it would be understood by a person having ordinary skill in the art at the time of the invention but generally refers to alkali metal ion cells, including lithium ion cells and sodium ion cells.

[0126] The term “ceramic saggar” should be given its ordinary meaning as it would be understood by a person having ordinary skill in the art at the time of the invention but generally refers to a ceramic substrate or tray used to hold materials fired during sintering. Saggar may be comprised of alumina ceramic, cordierite ceramic, mullite ceramic, silicon carbide, or zirconia.

[0127] The phrases “consisting essentially of’ or “consists essentially of’ are to be interpreted as limiting to the specified materials or steps involved (depending on context) but also to include - and not to exclude - any materials or steps that do not materially affect the basic and novel characteristics of the materials or steps involved.

[0128] Furthermore, embodiments of the present disclosure may refer to a coin cell, but any form factor or shape may be used for the incorporation of cathode materials produced herein. For example, the cathode materials may be incorporated in coin cells, pouch cells, prismatic cells, button cells, cylindrical cells, AA / AAA / C / D / 9-volt cells, lithium polymer cells or any other form factor.

[0129] The term “rock-salt” should be given its ordinary meaning as it would be understood by a person having ordinary7skill in the art at the time of the invention and refers to a phase having a cubic rock-salt crystal structure that is absent of cation layering order.

[0130] The term “cubic spinel” should be given its ordinary meaning as it would be understood by a person having ordinary skill in the art at the time of the invention and refers to a phase having a cubic spinel crystal structure that has a three-dimensional tunnel structure. A cubic spinel structure of the general formula DE2X4 (where D and E each represent one or more kinds of cations, and X represents a type of anion) has the same structure as the mineral spinel (MgAhCh), where the X anions form a face centered cubic lattice, the D cations reside in one eighth of the tetrahedral sites formed by the oxygen lattice and the E cations reside inhalf of the octahedral sites formed by the anion lattice. A substance having cubic spinel structure may also be described as a ciystal structure having the general formula DE2X4 and having space group symmetry Fd-3m in which the D cations reside in the 8b sites, the E cations reside in the 16c sites and the X anions reside in the 32e sites.

[0131] Unless stated otherwise all experiments and processes herein were performed under standard atmospheric pressure.EXAMPLES

[0132] Some aspects of the embodiments discussed above are disclosed in further detail in the following examples, which are not in any way intended to limit the scope of the present disclosure. Those in the art will appreciate that many other embodiments also fall within the scope of the disclosure, as it is described herein above and in the claims. The following are exemplary in nature to better illustrate the present disclosure and are non-limiting in scope, application or uses.

[0133] Material characterization

[0134] Scanning electron microscope (SEM) images and Energy-dispersive X-ray spectroscopy (EDX) mapping images were taken using a Phenom XL G2 Desktop SEM with an accelerating voltage of 15 kV under a back scattering electron mode. Powder samples were prepared by adhering onto a sample stub using conductive carbon tape.

[0135] X-ray diffraction (XRD) patterns of powders were measured by a Bruker D8 Advance diffractometer with a Cu Kot X-ray source and a diffracted beam monochromator. Rietveld refinement was done on the measured XRD patterns to quantify the amount of cation mixing: Ni in the Li layers using Ri erica software.

[0136] Lithium residuals of powders were measured by a Mettler Toledo Titrator Excellence T5. Samples were prepared by flocculating in deionized water and titrated with 0.1 M of HC1 solution to determine LiOH and Li2CCh contents on the surface of materials.

[0137] The porosity of a pellet was calculated from the following equation:Bulk densityPorosity = 1 — ( Particle density where bulk densify is mass of the pellet per given volume and particle densify is calculated from the theoretical mass densify of the precursor mixture.

[0138] The theoretical mass densify was calculated from the following equation:Where: n= number of atoms per unit cellA= atomic weight of atoms in the unit cellV= volume per unit cellN = Avogadro’s number (6.023E23)

[0139] Apparent porosity generally refers to the number of pores on the surface of an object. The apparent porosity of a saggar can be calculated from the following equation:Where:W=saturated massD=Dry massS= suspended mass

[0140] Cell preparation and electrochemical evaluation

[0141] Electrode slurries were prepared by mixing of active material, carbon black, and polyvinylidene fluoride (PVDF) in a weight ratio of 0.94: 0.04: 0.02 in N-Methyl-2- Pyrrolidone (NMP) with a solid content of 50 % using a planetary mixer. The slurry was coated onto 15 pm aluminum foil sheet using the doctor blade method and dried on a 90 °C drying table in air before final drying in a vacuum oven at 140 °C overnight. The dried electrodes were compressed using by calendar rolling and punched with a 13.00 mm diameter. The areal active mass loading was -18-22 mg / cm2Coin-cells were fabricated in an Argon filled glovebox with one sheet of active electrode, Li foil counter electrode. 2 layers of separator (Celgard 2500), and 100 pL of 1 .2 M LiPFe in a solution of ethylene carbonate: ethylmethyl carbonate: dimethyl carbonate (EC:EMC:DMC (25:5:70 wt%)) electrolyte using CR2032 coin-type casings. Galvanostatic cycling measurements were made using a Neware battery tester at a controlled temperature of 25 °C.Example 1 : Effect of pelletization of precursor mixture

[0142] The precursor mixture was prepared by mixing of Ni powder, Co powder, M CU powder, Zr(OH)4 powder, and 20 % excess Li2CO3 powder in a stoichiometric ratio of Li[Nio.83Mno.o6Coo.n]o.9975Zro.oo2502 (NMC83) in a high-speed mixer (100L, BaiHeLing). 2 kg of the mixed precursor was transferred into a ceramic porous saggar without pelletization (Figure la). For the pelletized precursor mixture, 125 g of the mixed precursor w as pelletizedusing a hydraulic press and a die set having a die diameter of 2’" (5.08 cm), then the pellet is transferred to a ceramic saggar (Figure lb). Sixteen pelletized samples were prepared, and the total amount of powder was 2 kg, to replicate the non-pelletized sample in weight. The saggar used in this example had a 23.4 % apparent porosity. The non-pelletized and pelletized samples are labelled as SI and S2 materials, respectively. The SI and SI samples were then both sintered at a max temperature of 900 °C under an oxygen atmosphere in a box furnace (KSF- 20-1 IQ). The S I and S2 sintered materials were then jet- milled to de-agglomerate secondary particles before characterization and electrochemical measurements. Figure 2 shows that both samples (S 1 and S2) have a single crystal morphology' with a smooth surface.

[0143] Figure 3 shows the XRD patterns of both SI and S2 samples having a pure single phase layered 03 phase without Li impurities. The main peak intensity (003) at 18° as well as peak separation (108) / (l 10) at 65° of S2 material are higher and well-developed compared to SI material. The cation mixing values determined from Rietveld refinement were 2.65 % and 1.08 % for SI and S2 samples, respectively. This indicates that the pelletization can provide material with higher crystallinity and homogeneity’, and possibly reduce the lithium loss for the Li-deficient composition where lithium is lost into the porous substrate. Figure 4 shows the first cycle charge-discharge profile of SI and S2 incorporated into a coin cell, tested between 2.8-4.3 V vs. Li+ / Li (y-axis) at C / 20 (the discharge at a rate equivalent to battery’ capacity discharged in 20 hours). The reversible discharge capacities were 188.6 (±0.4) and 194.7 (±0.2) mAh / g, whilst the first cycle irreversible capacities were 14.2 (±0.4) and 12.7 (±0.3) % for SI and S2 materials, respectively. Figure 5(a) and 5(b) show the charge-discharge cycling of half-cells tested at C / 20 formation for 2 cycles, followed by C / 5 for 23 cycles. The C / 5 capacity and capacity retention of S2 material were higher than S I material. Thus, the pelletized sample, S2. exhibited superior discharge capacity and capacity retention over a period of 25 charge / discharge cycles. The superior performance of S2 material is generally attributed to the better transition metal oxidation and interdiffusion from the pelletization technique.Example 2: Effect of pelletization pressure on precursor mixture

[0144] In this example, the pressure of the pelletization process was systematically investigated. Firstly, the NMC83 precursor mixture was prepared by mixing of Ni powder, Co powder, M CL powder, Zr(OH)4 powder, and 10% excess LizCCh in a stoichiometric ratio of Li[Nio.83Mno.o6Coo.n]o.9975Zro.oo2502 in a high-speed mixer. 125 g of the mixed precursor was pelletized using a hydraulic press and a die set using hand-pressed (S3) and applied forces of1 ton (4.84 MPa) (S4), 2.5 tons (12.09 MPa) (S5), and 4 (19.35 MPa) (S6) tons. The samples were transferred onto a 23.4% apparent porosity saggar piece for sintering in a tube furnace. The maximum sintering temperature was carried out at 900 °C under an oxygen atmosphere. The sintered materials were jet-milled to de-agglomerate secondary particles before characterization and electrochemical measurements.

[0145] Figure 6 shows that all samples exhibited a uniform single crystal morphology with a smooth surface. There were no particle agglomerations observed in all the samples. Figure 7(a) shows that the cation mixing obtained from Rietveld refinement increased with increasing pressures (from S4 to S6). The cation mixing values were 1.5%, 0.79%, 1.16% and 1.63% for S3, S4, S5 and S6 samples, respectively. S3 material was pelletized under reduced pressures such that transition metal interdiffusion may have been limited during sintering. However, the S6 material was densely pelletized such that oxygen diffusion and transition metal diffusion may have been hindered since the majority of feedstocks used were in elemental form. The porosity of S6 pelletized precursor prior to sintering was 66% while the porosity of S3 was about 70%. For lithium residues determined by titration. Figure 7(b) shows increasing pelletized pressure led to a reduction of surface lithium impurities (LiOH (solid points) and Li2COs (unfilled points)), particularly the lithium hydroxide. However, the level of surface impurities was low and can be removed by re-pelletization and refiring. Figure 8 shows the charge-discharge cycling of half-cells tested at C / 20 formation for 2 cycles, followed by C / 5 for 23 cycles. The cut-off voltage was 2.8-4.3 V vs. Li / Li at C / 20. All samples showed similar discharge capacities at C / 20 with somewhat varying capacity at C / 5, however, capacity retention varied significantly between samples, as shown in Figure 8(b). The electrochemical result indicates that the pelletization process significantly influenced the properties of positive electrode materials.Example 3: Dopant distribution

[0146] An NMC83 precursor mixture was prepared by mixing of Ni powder, Co powder, MnsCL powder, Zr(OH)4 powder, and 20% excess Li2COs in a stoichiometric ratio of Li[Nio.83Mno.o6Coo.n]o.99Zro.oi02 in a coffee grinder. 1 mol% of Zr doping was intentionally used as it will potentially limit transition metal interdiffusion and crystal growth. Both pelletized sample (S7) and non-pelletized sample (S8) w ere prepared. For the pelletization, 100 g of the mixed precursor was pelletized at 5 tons using a hydraulic press and a die set. Both samples were then transferred onto a 23.4% apparent porosity saggar piece for sintering in a tube furnace. The sintering was carried out at a maximum temperature of 900 °C under anoxygen atmosphere. Figure 9 shows the SEM images on both samples after sintering and before deagglomeration or pulverization. It can be clearly observed that the non-pelletized material (S 8) contained large amounts of agglomerates. The high level of Zr dopant and numerous void spaces between feedstocks in the S8 material were thought to limit lithiation kinetics. The agglomeration of S8 necessitates a more intense deagglomeration process which significantly affects the process throughput. On the other hand, pelletized material (S7) showed single crystal morphology and uniform particle size even without deagglomeration. Thus, the dopant was optimally distributed through throughout the sintered pellet. After deagglomeration of the pellet by jet-milling, Figure 10 shows that both samples exhibited similar morphology' of single crystal with a smooth surface. Figure 11 shows the XRD patterns of both samples having a pure single phase layered 03 phase without Li impurities. The main peak intensity (003) at 18° as well as peak separation (108) / (l 10) at 64°-65° of S7 material were higher and well- developed indicating of a very high crystallinity'. The cation mixing values determined by Rietveld refinement were 1.0 and 4.93 % for S7 and S8 materials, respectively . The results indicate that pelletization significantly improved material homogeneity’ and lithiation. Figure 12 shows the (a) discharge capacity and (b) capacity retention at C / 5 of coin-cells made with S7 and S8 materials.Example 4: Pelletization with LiOH-FLO

[0147] To demonstrate that pelletization can enhance lithiation kinetics, the NMC83 precursor mixture w as prepared by mixing of Ni powder, Co powder, MmOr powder, Zr(OH)4 powder, and 10% excess LiOH-ELO in a stoichiometric ratio of Li[Nio.83Mno.o6Coo.n]o.9975Zro.oo2502 in a coffee grinder. The mixed precursor powder was split into three groups, S9, S10, and Si l. S9 was not pelletized and transferred to alumina container with no porosity. S10 was not pelletized and transferred to a porous substrate with 23.4 % apparent porosity. Finally, Si l was pelletized and placed onto a porous ceramic saggar substrate having a porosity' of 23.4 % . The sintering was done at a maximum temperature at 900 °C under oxygen atmosphere in a tube furnace. As shown in Figure 13a, the non-pelletized S9 material exhibited an XRD pattern of a pure single phase layered 03 phase. The main peak intensity (003) at 18° as well as peak separation ( 108) / ( 110) at 65° are high and well-developed. However, S10 material showed the characteristic peak of a Li-deficient NMC material, indicating that the lithium was lost into the porous substrate. The (108) / (l 10) peak separation was not observed. When the precursor was pelletized (SI 1), the XRD pattern was identical to the non-pelletized sample on a non-porous container (S9). The results indicate that thepelletization enhances lithiation kinetics and reduces Li loss into porous saggar, especially for the all-dry cathode material synthesis where several feedstocks are mixed.Additional Notes

[0148] It should be appreciated that all combinations of the foregoing concepts and additional concepts discussed in greater detail below (provided such concepts are not mutually inconsistent) are contemplated as being part of the inventive subject matter disclosed herein. In particular, all combinations of claimed subject matter appearing at the end of this disclosure are contemplated as being part of the inventive subject matter disclosed herein. It should also be appreciated that terminology' explicitly employed herein that also may appear in any disclosure incorporated by reference should be accorded a meaning most consistent with the particular concepts disclosed herein.

[0149] Reference throughout the specification to “one example’’, “another example”, “an example”, and so forth, means that a particular element (e.g., feature, structure, and / or characteristic) described in connection with the example is included in at least one example described herein, and may or may not be present in other examples. In addition, it is to be understood that the described elements for any example may be combined in any suitable manner in the various examples unless the context clearly dictates otherw ise.

[0150] It is to be understood that the ranges provided herein include the stated range and any value or sub-range within the stated range, as if such value or sub-range were explicitly recited. For example, a range from about 2 nm to about 20 nm should be interpreted to include not only the explicitly recited limits of from about 2 nm to about 20 nm, but also to include individual values, such as about 3.5 nm, about 8 nm, about 18.2 nm, etc., and sub-ranges, such as from about 5 nm to about 10 nm, etc. Furthermore, when “about” and / or “substantially” are / is utilized to describe a value, this is meant to encompass minor variations (up to + / - 10%) from the stated value.

[0151] While several examples have been described in detail, it is to be understood that the disclosed examples may be modified. Therefore, the foregoing description is to be considered non-limiting.

[0152] While certain examples have been described, these examples have been presented by way of example only, and are not intended to limit the scope of the disclosure. Indeed, the novel methods and systems described herein may be embodied in a variety' of other forms. Furthermore, various omissions, substitutions and changes in the systems and methods described herein may be made without departing from the spirit of the disclosure. Theaccompanying claims and their equivalents are intended to cover such forms or modifications as would fall within the scope and spirit of the disclosure.

[0153] Features, materials, characteristics, or groups described in conjunction with a particular aspect, or example are to be understood to be applicable to any other aspect or example described in this section or elsewhere in this specification unless incompatible therewith. All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and / or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and / or steps are mutually exclusive. The protection is not restricted to the details of any foregoing examples. The protection extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.

[0154] Furthermore, certain features that are described in this disclosure in the context of separate implementations can also be implemented in combination in a single implementation. Conversely, various features that are described in the context of a single implementation can also be implemented in multiple implementations separately or in any suitable sub-combination. Moreover, although features may be described above as acting in certain combinations, one or more features from a claimed combination can, in some cases, be excised from the combination, and the combination may be claimed as a sub-combination or variation of a sub-combination.

[0155] Moreover, while operations may be depicted in the drawings or described in the specification in a particular order, such operations need not be performed in the particular order shown or in sequential order, or that all operations be performed, to achieve desirable results. Other operations that are not depicted or described can be incorporated in the example methods and processes. For example, one or more additional operations can be performed before, after, simultaneously, or between any of the described operations. Further, the operations may be rearranged or reordered in other implementations. Those skilled in the art will appreciate that in some examples, the actual steps taken in the processes illustrated and / or disclosed may differ from those shown in the figures. Depending on the example, certain of the steps described above may be removed or others may be added. Furthermore, the features and attributes of the specific examples disclosed above may be combined in different ways to form additional examples, all of which fall within the scope of the present disclosure. Also, the separation of various system components in the implementations described above shouldnot be understood as requiring such separation in all implementations, and it should be understood that the described components and systems can generally be integrated together in a single product or packaged into multiple products.

[0156] For purposes of this disclosure, certain aspects, advantages, and novel features are described herein. Not necessarily all such advantages may be achieved in accordance with any particular example. Thus, for example, those skilled in the art will recognize that the disclosure may be embodied or carried out in a manner that achieves one advantage or a group of advantages as taught herein without necessarily achieving other advantages as may be taught or suggested herein.

[0157] Conditional language, such as “can,” “could,” “might,” or “may,” unless specifically stated otherwise, or otherwise understood within the context as used, is generally intended to convey that certain examples include, while other examples do not include, certain features, elements, and / or steps. Thus, such conditional language is not generally intended to imply that features, elements, and / or steps are in any way required for one or more examples or that one or more examples necessarily include logic for deciding, with or without user input or prompting, whether these features, elements, and / or steps are included or are to be performed in any particular example.

[0158] Conjunctive language such as the phrase “at least one of X, Y, and Z,” unless specifically stated otherwise, is otherwise understood with the context as used in general to convey that an item. term. etc. may be either X, Y. or Z. Thus, such conjunctive language is not generally intended to imply that certain examples require the presence of at least one of X, at least one of Y, and at least one of Z.

[0159] Language of degree used herein, such as the terms “approximately,” “about.” “generally,” and “substantially” represent a value, amount, or characteristic close to the stated value, amount, or characteristic that still performs a desired function or achieves a desired result.

[0160] The scope of the present disclosure is not intended to be limited by the specific disclosures of preferred examples in this section or elsewhere in this specification and may be defined by claims as presented in this section or elsewhere in this specification or as presented in the future. The language of the claims is to be interpreted broadly based on the language employed in the claims and not limited to the examples described in the present specification or during the prosecution of the application, which examples are to be construed as non-exclusive.

[0161] Although the foregoing invention has been described in terms of certain preferred embodiments, other embodiments will be apparent to those of ordinary skill in the art. Additionally, other combinations, omissions, substitutions, and modifications will be apparent to the skilled artisan, in view of the disclosure herein. Accordingly, the present invention is not intended to be limited by the recitation of the preferred embodiments but is instead to be defined by reference to the appended claims. All references cited herein are incorporated by reference in their entirety.

[0162] The terminology used in the description presented herein is not intended to be interpreted in any limited or restrictive manner and unless otherwise indicated refers to the ordinary meaning as would be understood by one of ordinary skill in the art in view of the specification. Furthermore, embodiments may comprise, consist of, consist essentially of, several novel features, no single one of which is solely responsible for its desirable attributes or is believed to be essential to practicing the embodiments herein described. As used herein, the section headings are for organizational purposes only and are not to be construed as limiting the described subject matter in any way. All literature and similar materials cited in this application, including but not limited to. patents, patent applications, articles, books, treatises, and internet web pages are expressly incorporated by reference in their entirety for any purpose. When definitions of terms in incorporated references appear to differ from the definitions provided in the present teachings, the definition provided in the present teachings shall control. It will be appreciated that there is an implied “about” prior to the temperatures, concentrations, times, etc. discussed in the present teachings, such that slight and insubstantial deviations are within the scope of the present teachings herein.

[0163] Although this disclosure is in the context of certain embodiments and examples, those of ordinary skill in the art will understand that the present disclosure extends beyond the specifically disclosed embodiments to other alternative embodiments and / or uses of the embodiments and obvious modifications and equivalents thereof. In addition, while several variations of the embodiments have been shown and described in detail, other modifications, which are within the scope of this disclosure, will be readily apparent to those of ordinary skill in the art based upon this disclosure. It is also contemplated that various combinations or sub-combinations of the specific features and aspects of the embodiments may be made and still fall within the scope of the disclosure. It should be understood that various features and aspects of the disclosed embodiments can be combined with, or substituted for, one another in order to form varying modes or embodiments of the disclosure. Thus, it isintended that the scope of the present disclosure herein disclosed should not be limited by the particular disclosed embodiments described above.

Claims

WHAT IS CLAIMED IS:

1. A method of preparing a lithium transition metal oxide positive electrode material for a batten , the method comprising:(a) preparing a precursor mixture by mixing a stoichiometric amount of one or more transition metal feedstocks, one or more lithium sources, and one or more dopants in a liquid-free environment;(b) pelletizing the precursor mixture into one or more pellets under pressures of at least about 0. 1 MPa; and(c) heating the pelletized precursor mixture on a substrate to produce the lithium transitional metal oxide positive electrode material.

2. The method of claim 1, wherein the one or more transition metal feedstocks and the one or more dopants are selected from the group consisting of: elemental metal, oxides, hydroxides, oxy hydroxides, carbonates, sulfates, nitrates, acetates, and combinations thereof.

3. The method of claim 1, wherein the one or more lithium sources are selected from the group consisting of: Li carbonate, Li oxide. Li hydroxide, Li hydroxide monohydrate. Li acetate, Li chloride, Li fluoride, Li nitrate, Li sulfate, and mixtures thereof.

4. The method of claim 1 , wherein the one or more dopants are selected from the group consisting of: Na, B, Al, Mg, Zr, Nb. Fe. Si, P, Mo, Ba, Sr, Ca, Zn, Cr, V, W, Nd, La, Cs. Ta. Ce. Cu, Eu, Ti. Sn. Sb. Pb. Bi. Rb. and mixtures thereof.

5. The method of claim 1 , wherein the precursor mixture is pelletized using a hydraulic press.

6. The method of claim 5, wherein the lithium transitional metal oxide positive electrode material is selected from the group consisting of NMC, NCA, LMO, LFP, LNMO, LMO, and LCO.

7. The method of claim 5, wherein the pressure applied to the pelletized mixture through hydraulic press is in a range of about 0. 1-100 MPa.

8. The method of claim 5, wherein the pellet is in the shape of a cylinder, sphere, cone, pyramid, prism, cuboid, cube, or a combination thereof.

9. The method of claim 7, wherein the pellet has a porosity of about 5-90 % prior to the heating.

10. The method of claim 1. wherein the substrate is porous ceramic saggar that has an apparent porosity ranging from about 0-50%.

11. The method of claim 1, wherein heating the pelletized precursor mixture is carried out under an atmosphere of inert gas, oxygen, a reduced oxygen partial pressure gas, dry air, or air.

12. The method of claim 1, wherein the heating temperature is in a range between about 450-1100 °C.

13. The method of claim 1, wherein heating is carried out with one or more temperature holds.

14. The method of claim 1, additionally comprising pulverizing the heated pelletized precursor mixture through at least one of impact milling, jet milling, or grinding to produce pulverized material.

15. The method of claim 14, wherein the method further comprises mixing the pulverized material with one or more coating materials or one or more additional lithium sources to produce coated material.

16. The method of claim 15, wherein the method further comprises repelletizing the coated material to produce repelletized material.

17. The method of claim 16, wherein the method further comprises reheating the repelletized material.

18. A Li-ion battery comprising an electrode material comprising: a lithium transition metal oxide material produced from the method of claim 1.

19. An all-dry method for preparing a positive electrode material for a battery, the method comprising: preparing a precursor mixture by mixing a stoichiometric amount of nickel, manganese, and cobalt metal feedstocks, one or more lithium sources, and one or more optional dopants in a liquid-free environment; mechanically compressing the precursor mixture into a compressed material having a porosity of about 5-90 %; and heating tire compressed precursor mixture at temperatures exceeding 700 degrees Celsius to produce the positive electrode material.

20. Tire method of Claim 19, wherein tire one or more dopants are present and selected from the group consisting of: Na, B, Al, Mg, Zr, Nb, Fe, Si, P, Mo, Ba, Sr, Ca, Zn, Cr, V, W, Nd, La, Cs, Ta, Ce, Cu, Eu, Ti, Sn, Sb, Pb, Bi, Rb, and mixtures thereof.

21. The method of Claim 20, wherein the one or more dopants comprise Zr.

22. The method of Claim 20, wherein the positive electrode material consists essentially of particles that have single crystal morphology.

23. The method of Claim 20, wherein the positive electrode material consists essentially of particles that have uniform particle size without deagglomeration.

24. The method of Claim 20, wherein the one or more dopants are present and configured to limit transition metal interdiffusion.

25. The method of Claim 20, wherein the positive electrode material has a porosityless than about 30%.

26. A pelletized cathode formulation comprising: a pellet containing a precursor mixture with a stoichiometric amount of one or more transition metal feedstocks, one or more lithium sources, and optionally one or more dopants; wherein the pellet is substantially free of solvents and solvent residues; wherein the pellet has a porosity less than about 70%; wherein the porosity of the pellet is calculated from the following equation:Bulk density .Porosity = 1 — ( Particle density where bulk density is mass of the pellet per given volume and particle density is calculated from the theoretical mass density of the precursor mixture.

27. The pelletized cathode formulation of Claim 26, wherein the pellet contains a stoichiometric amount of lithium, nickel, manganese, and cobalt for an LifNiMnCo] cathode material.

28. The pelletized cathode formulation of Claim 26, wherein the pellet is free of iron.

29. The pelletized cathode formulation of Claim 26, wherein the pelletized cathode formulation includes zirconium.

30. The pelletized cathode formulation of Claim 26, wherein the pellet contains a stoichiometric amount of materials represented by the formula:Lll+x[(NlnMnmCOc)l-a a] l-xO2, where:-0.03 < x < 0.06; n + m + c = 1; n > 0.05; m > 0.05; c > 0.05;A is a metal dopant; and 0 < a < 0.05.

31. The pelletized cathode formulation of Claim 26, wherein the pellet contains a stoichiometric amount of materials represented by the formula Li[Ni0.83Mn0.06CO0.11]0.9975Zr0.0025O2.

32. The pelletized cathode formulation of Claim 26, wherein the pellet contains a stoichiometric amount of materials represented by the formula Lii+x[(NinCocAlm)i-aAa]i-xO2 where:A is selected from the group consisting of Mg, Si, Ca, Ti, V. Zn, Sr. Zr. Nb, Mo, Sn. Sb, Ba, and combinations thereof;-0.05 <x < 0.10; n + m + c = 1; and0 < a < 0.05.

33. The pelletized cathode formulation of Claim 26, wherein the pellet contains a stoichiometric amount of materials represented by the formula LixM -y-zNiyMzCh where:M is selected from the group consisting of Mg, Al, Si, Ca, Ti, V, Co, Zn, Sr, Zr, Nb, Mo. Sn, Sb, Ba, and combinations thereof;0.25 < x < 1.1;0.3 < y < 0.5; and0 < z < 0.15.

34. The pelletized cathode formulation of Claim 33, wherein the pelletized cathode formulation is configured for the production of a cathode material having a cubic spinel structure with single crystalline morphologies.

35. The pelletized cathode formulation of Claim 26, wherein the pelletized cathode formulation consists essentially of a cathode material having a having a single crystalline rock salt structure.

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