Method for preparing a lithium nickel manganese cobalt oxide cathode material and product thereof

Abstract

Disclosed herein are methods of preparing lithium nickel manganese cobalt oxide precursor particulates, methods of preparing lithium nickel manganese cobalt oxide cathode materials, and the products thereof. In some examples lithium nickel manganese cobalt oxide precursor particulates have a majority cubic spinel phase. In some examples the lithium nickel manganese cobalt oxide precursor particulates and the lithium nickel manganese cobalt oxide cathode materials are mixed and combined according to dry processes.

Description

NOVBS.016WO PATENT METHOD FOR PREPARING A LITHIUM NICKEL MANGANESE COBALT OXIDE CATHODE MATERIAL AND PRODUCT THEREOF INCORPORATION BY REFERENCE TO ANY PRIORITY APPLICATIONS

[0001] This PCT application claims priority to U.S. Provisional Application 63 / 600940, filed November 20, 2023, the entirety of which is incorporated herein for any and all purposes. BACKGROUND Field

[0002] This disclosure relates to battery cathode materials including lithium nickel manganese cobalt oxide cathode materials. Related Art

[0003] The development of rechargeable high energy density batteries, such as Li-ion batteries, is of great technological importance. Typically, commercial rechargeable Li-ion batteries use a lithium transition metal oxide cathode and a graphite anode. While batteries based on such materials are approaching their theoretical energy density limit, significant research and development continues in order to improve other important characteristics such as cycle life, efficiency, and cost. Further, significant research and development continues in order to simplify the methods of production and to reduce the complexity, material amounts, and losses involved.

[0004] Insertion compound transition metal oxide cathode materials for use in lithium rechargeable batteries can comprise lithium, one or more Ni, Mn or Co, oxygen, and optional metal dopants (e.g. Mg, Al, Ti, Zr, W, Zn, Mo, K, Na, Si, Ta) and such materials can be further coated with other materials (e.g. Al2O3, ZrO2, TiO2). For ease of manufacturing, an air stable version of the transition metal oxide can be employed. Given the substantial demand for these batteries, it is of great importance to be able to provide significant and economic supplies of such materials.

[0005] One method of preparing LiNMC (including SC-LiNMC) is to first make a mixed metal hydroxide (MMH) precursor particulate or a mixed metal carbonate (MMC) precursor particulate of Ni, Mn, Co, and optional metal dopant A, each inproportion according to the desired final LiNMC composition. The MMH or MMC precursor particulate is made by co-precipitation of metal salts in an aqueous solution, followed by filtering, drying, and grinding steps. The resulting MMH or MMC precursor particulate is then ground together with a lithium source (e.g., LiOH, LiOH‧H2O or Li2CO3), typically in an amount that is in excess of the desired LiNMC composition to form a mixture. The mixture is then sintered in air at temperatures in the range of 600 - 1000 °C. A description of the synthesis of LiNMC by this method can be found in Journal of The Electrochemical Society, 165 (5) A1038-A1045 (2018). A two-step heating method can also be employed, as described in WO 2019 / 185349. The co-precipitation method may be used because it produces MMH or MMC precursor particulate that have a particle size larger than 100 nm. Smaller particle sizes create problems with dust and particle handling, making processing more costly. In addition, the co-precipitation method is used because it achieves atomic-scale mixing of the transition metals in the MMH or MMC. This is desirable, since the transition metals can diffuse slowly during sintering, resulting in the formation of unwanted impurity phases in the LiNMC formed after sintering. Therefore, if atomic mixing is not achieved in the MMH or MMC, then long sintering times may be required to convert the MMH or MMC precursor particulates to the desired single-phase LiNMC, which can increase cost. Lithium loss via evaporation also commonly occurs during the sintering step, making long sintering times undesirable. Co-precipitation methods also require many steps and can produce large amounts of wastewater. In addition, the co-precipitation method requires that the sources of transition metals are soluble metal salts, which can be more expensive than insoluble sources of these metals, such as metal oxide, hydroxide and carbonate compounds.

[0006] Conventionally, the precursor particulate made by the co-precipitation process to make LiNMC or used in dry processes to make LiNMC has the same Ni:Mn:Co molar ratio as the product LiNMC.

[0007] The above information disclosed in this Background section is only for enhancement of understanding of the background and therefore the information discussed in this Background section does not necessarily constitute prior art. SUMMARY

[0008] In some aspects, the techniques described herein relate to a method of preparing a lithium nickel manganese cobalt oxide cathode material having the formula Li1+p[(NinMnmCoc)1-aAa]1-pO2, where -0.03 ≤ p ≤ 0.06; n + m + c = 1; n ≥ 0.50; m ≥ 0.05; c≥ 0; A is an optional metal dopant; and 0 ≤ a ≤ 0.05; the method including: obtaining feedstock components that include a nickel source, a manganese source, and a cobalt source; combining the feedstock components in a feedstock component Ni:Mn:Co:A molar ratio of x:y:z:w, where x + y + z = 1, x ≥ 0, 0.10 ≤ y ≤ 0.90, z ≥ 0, and 0 ≤ w ≤ 0.05 to produce a feedstock mixture; heating the feedstock mixture in an oxygen containing atmosphere to a temperature greater than about 450°C according to a feedstock mixture heating procedure to obtain a precursor particulate; combining precursor components that include the precursor particulate, a lithium source, and a second nickel source to obtain a precursor mixture, wherein the precursor components are combined such that the total amount of Ni, Mn, Co, and dopant A, are substantially equal to the stoichiometric amounts required to make the lithium nickel manganese cobalt oxide cathode material and in which the lithium is greater than or equal to the stoichiometric amounts required to make the lithium nickel manganese cobalt oxide cathode material; and heating the precursor mixture in an oxygen containing atmosphere at a temperature greater than about 700°C according to a precursor mixture heating procedure to obtain the lithium nickel manganese cobalt oxide cathode material.

[0009] In some aspects, the techniques described herein relate to a method wherein c ≥ 0.05.

[0010] In some aspects, the techniques described herein relate to a method wherein z > 0.4.

[0011] In some aspects, the techniques described herein relate to a method wherein x + y + z = 1, 0 ≤ w ≤ 0.05, and wherein the Ni, Mn, and Co content of the precursor particulate composition is defined to be within the region of the Ni-Mn-Co ternary composition diagram bounded by the line segments ακ, κν, νδ, δε, εξ, and ξα where α = Mn0.2Co0.8, κ = Mn0.8Co0.2, ν = Ni0.2Mn0.8, δ = Ni0.47Mn0.53, ε = Ni0.47Mn0.36Co0.17, and ξ = Ni0.8Co0.2.

[0012] In some aspects, the techniques described herein relate to a method wherein x + y + z = 1, 0 ≤ w ≤ 0.05, and where the Ni, Mn, and Co content of the precursor particulate composition is defined to be within the region of the Ni-Mn-Co ternary composition diagram bounded by the line segments αβ, βγ, γδ, δε, εζ, ζη, and ηα where α = Mn0.2Co0.8, β = Mn0.5Co0.5, γ = Ni0.25Mn0.75, δ = Ni0.47Mn0.53, ε =ζ = Ni0.30Mn0.36Co0.34, and η = Ni0.1Mn0.1Co0.8.

[0013] In some aspects, the techniques described herein relate to a method wherein x + y + z = 1, 0 ≤ w ≤ 0.05, and where the Ni, Mn, and Co content of the precursorparticulate composition is defined to be within the region of the Ni-Mn-Co ternary composition diagram bounded by the line segments σβ, βγ, γτ, and τσ where σ = Mn0.3Co0.7, β = Mn0.5Co0.5, γ = Ni0.25Mn0.75, τ = Ni0.40Mn0.60.

[0014] In some aspects, the techniques described herein relate to a method wherein the precursor particulate consists essentially of a spinel phase.

[0015] In some aspects, the techniques described herein relate to a method wherein the precursor spinel phase contains all of the Mn and Co required to synthesize the lithium nickel manganese cobalt oxide cathode material.

[0016] In some aspects, the techniques described herein relate to a method, wherein the precursor components additionally include a second cobalt source.

[0017] In some aspects, the techniques described herein relate to a method, wherein the combining to obtain a feedstock mixture is a dry mixing process.

[0018] In some aspects, the techniques described herein relate to a method, wherein the dry mixing process is a dry trituration process and the precursor mixture is substantially free of solvent residue.

[0019] In some aspects, the techniques described herein relate to a method, additionally including adding a flux during the heating of the feedstock mixture or the precursor mixture.

[0020] In some aspects, the techniques described herein relate to an all-dry method of preparing a lithium nickel manganese cobalt oxide material, the method including: obtaining feedstock components that include a nickel source, a manganese source, and a cobalt source; dry mixing the feedstock components to obtain a feedstock mixture, wherein the molar amount of Ni is about 47% or less than of the molar amounts of manganese and cobalt individually; heating the feedstock mixture an oxygen containing atmosphere from a temperature below about 50°C to an elevated temperature between about 700°C to about 1200°C and holding at the elevated temperature for at least an hour; cooling the feedstock mixture to a temperature below about 100°C to obtain a nickel manganese cobalt oxide precursor particulate having a majority phase of cubic spinel oxide.

[0021] In some aspects, the techniques described herein relate to a method, additionally including dry mixing the nickel manganese cobalt oxide precursor particulate with a lithium source and a second nickel source to obtain a precursor mixture.

[0022] In some aspects, the techniques described herein relate to a method, additionally including heating the precursor mixture in an oxygen containing atmosphere from a temperature below about 50°C to one or more elevated temperatures between about700°C to about 1600°C and holding at the one or more elevated temperatures for at least an hour followed by cooling to below about 50°C to obtain a lithium nickel manganese cobalt oxide cathode material.

[0023] In some aspects, the techniques described herein relate to a method, wherein the lithium nickel manganese cobalt oxide cathode material has the formula LiNi0.6Mn0.2Co0.2O2.

[0024] In some aspects, the techniques described herein relate to a method, additionally including deagglomerating the nickel manganese cobalt oxide cathode material.

[0025] In some aspects, the techniques described herein relate to a method, wherein the molar amount of Ni is about 20% or less than of the molar amounts of manganese and cobalt individually.

[0026] In some aspects, the techniques described herein relate to a nickel manganese cobalt oxide precursor particulate including: a cubic spinel oxide phase as the majority phase; wherein the Ni, Mn, and Co content of the nickel manganese cobalt oxide precursor particulate is within the region of the Ni-Mn-Co ternary composition diagram bounded by the line segments ακ, κν, νδ, δε, εξ, and ξα where α = Mn0.2Co0.8, κ = Mn0.8Co0.2, ν = Ni0.2Mn0.8, δ = Ni0.47Mn0.53, ε = Ni0.47Mn0.36Co0.17, and ξ = Ni0.8Co0.2; wherein the nickel manganese cobalt oxide precursor particulate is free of solvents and solvent residues; wherein the nickel manganese cobalt oxide precursor particulate consists essentially of nickel manganese cobalt oxide precursor materials homogeneously distributed on an atomic scale.

[0027] In some aspects, the techniques described herein relate to a nickel manganese cobalt oxide precursor particulate, wherein the molar amount of Ni is about 20% or less than of the molar amounts of manganese and cobalt individually.

[0028] In some aspects, the techniques described herein relate to a nickel manganese cobalt oxide precursor particulate, wherein the Ni, Mn, and Co content of the precursor particulate composition is defined to be within the region of the Ni-Mn-Co ternary composition diagram bounded by the line segments αβ, βγ, γδ, δε, εζ, ζη, and ηα where α = Mn0.2Co0.8, β = Mn0.5Co0.5, γ = Ni0.25Mn0.75, δ =ε = Ni0.47Mn0.36Co0.17, ζ = Ni0.30Mn0.36Co0.34, and η = Ni0.1Mn0.1Co0.8.

[0029] In some aspects, the techniques described herein relate to a nickel manganese cobalt oxide precursor particulate, additionally including minority phases of rock-salt and tetragonal spinel.

[0030] In some aspects, the techniques described herein relate to a nickel manganese cobalt oxide precursor particulate, wherein the nickel manganese cobalt oxide precursor particulate consists essentially of cubic spinel oxide phase. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 illustrates a phase diagram of Ni-Mn-Co-oxides heated in air between 700°C and 800°C.

[0032] Figure 2 illustrates an Ni-Mn-Co composition diagram for some embodiments herein.

[0033] Figure 3 illustrates an Ni-Mn-Co composition diagram for some embodiments herein.

[0034] Figure 4 illustrates an Ni-Mn-Co composition diagram for some embodiments herein.

[0035] Figure 5 illustrates XRD patterns of precursor particulate samples from Examples 1-8. In the figure circles indicate XRD peaks from cubic spinel phases, triangles indicate peaks from tetragonal spinel phases, and squares indicate peaks from rock salt phases.

[0036] Figure 6(a) illustrates EDS compositional maps of Ni in precursor particulate samples from Examples 1-8. In these images the concentration of Ni is proportional to the brightness.

[0037] Figure 6(b) illustrates EDS compositional maps of Mn in precursor particulate samples from Examples 1-8. In these images the concentration of Mn is proportional to the brightness.

[0038] Figure 6(c) illustrates EDS compositional maps of Co in precursor particulate samples from Examples 1-8. In these images the concentration of Co is proportional to the brightness.

[0039] Figure 7 illustrates SEM images of LiNMC samples from Examples 9- 16.

[0040] Figure 8 illustrates XRD patterns of samples from Examples 9-16.

[0041] Figure 9 illustrates voltage curves of the first cycle for LiNMC from Examples 9-16.

[0042] Figure 10 illustrates capacity as a function of cycle number for LiNMC discharge curves for LiNMC samples from Examples 9-16.

[0043] Figure 11 illustrates SEM images of LiNMC from Examples 17-19.

[0044] Figure 12 illustrates XRD patterns of LiNMC from Examples 17-19.

[0045] Figure 13 illustrates voltage curves of the first cycle for LiNMC from Examples 17-19.

[0046] Figure 14 illustrates capacity as a function of cycle number for LiNMC from Examples 17-19.

[0047] Figure 15 illustrates a polyhedral representation of a cubic rock salt crystal structure.

[0048] Figure 16 illustrates a polyhedral representation of a cubic spinel crystal structure.

[0049] Figure 17 illustrates a flow chart according to some embodiments herein. DETAILED DESCRIPTION

[0050] Embodiments disclosed herein relate to an improved method of making LiNMC. In methods of some embodiments, a nickel source, a manganese source, and a cobalt source are combined to produce a feedstock mixture, which is then heated in an oxygen containing atmosphere to form a precursor particulate comprising a nickel, manganese, and cobalt oxide having a cubic spinel structure. The precursor particulate described by embodiments herein exhibits an excellent homogeneity in its components at the atomic level. The precursor particulate is then converted to LiNMC by heating in an oxygen containing atmosphere with a lithium source, a second nickel source, and, optionally, a second cobalt source. The resulting NMC is found to have excellent homogeneity in its components that is superior to LiNMC made from a rock-salt precursor and is furthermore similar to the homogeneity achievable by typical co-precipitation processes. As a result, the LiNMC made according to embodiments herein has superior electrochemical characteristics compared to LiNMC made from rock-salt precursors or other all-dry synthesis methods.

[0051] Lithium nickel manganese cobalt oxide particulate (LiNMC) type materials for use as cathodes in Li-ion batteries may have an O3 layered structure with the general actual formula Li1+p[(NinMnmCoc)1-aAa]1-pO2, where -0.03 ≤ p ≤ 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. In some cases LiNMC type materials for use as cathodes in Li-ion batteries can have an O3 layered structure and have the general actual formula Li1+p[(NinMnmCoc)1-aAa]1-pO2, where -0.03 ≤ p ≤ 0.06; n + m + c = 1; n ≥ 0.05; m ≥ 0.05; c ≥ 0; A is a metal dopant; and 0 ≤ a ≤ 0.05. Metal dopantsinclude Mg, Al and Zr or combinations thereof. High energy density LiNMC used in commercial applications have high Ni contents, such that n ≥ 0.6. Especially desirable in some applications are single crystal LiNMC lithium transition metal oxide particulate materials, abbreviated as SC-LiNMC and also known as monolithic “NMC”, in which the average LiNMC grain size exceeds 1 μm. If the grain size is too large, then increased impedance during Li-ion cell operation can result. Therefore, SC-LiNMC, grain sizes (D50) may be present between 1 μm and 20 μm. SC-LiNMC particles can consist of multiple LiNMC grains. However, superior capacity retention can be obtained if SC- LiNMC particles each consist of a single LiNMC grain.

[0052] The disclosure herein may be better understood through reference to a ternary composition diagram, such as that shown in Figure 1. Abe et al., Formation region of monophase with cubic spinel-type oxides in Mn Co Ni ternary system, Journal of Materials Science, 34 (1999) 4639-4634 (incorporated by reference herein) explored the ternary Ni-Mn-Co system in air at temperatures from 700°C to 1100°C. To do this they dissolved nitrate salts of Mn, Co, and Ni in water and then evaporated the solution to dryness. The solid residue was then collected and heated in air. This resulted in the formation of oxides. The structures of the oxide phases that were present were determined by x-ray diffraction. The results of these experiments are summarized in the ternary diagram shown in Figure 1. Figure 1 shows what phases are formed for the indicated metal ratios when those compositions are heated. The diagram has three regions. There is a Mn- rich region in which there is two-phase coexistence between oxides with a cubic spinel structure and tetragonal spinel structure. There is a Ni-rich region in which there is two- phase coexistence between oxides with a cubic spinel oxide structure and a rock-salt structure. Between the Mn-rich region and the Ni-rich region there is a single-phase region in which a cubic spinel with the formula (NixCoyMnz)3O4(x + y + z = 1) is the equilibrium phase. At 800°C the cubic spinel single-phase region is larger than at 1100°C. However, if the temperature is lowered to 700°C the boundaries of the single-phase region remain the same as the boundaries at 800°C. Therefore, it is not expected that the boundaries of the single-phase region are bigger than what is represented in Figure 1 using the preparation methods of Abe et al.

[0053] 2017 Jiang et al., Journal of Alloys and Compounds, 691 (2017) 206- 214 describes a method in which a co-precipitated hydroxide precursor is heated in air at 500°C to make a composition of (Ni0.29Co0.33Mn0.38)3O4. However, the method utilized a co-precipitation, which is not desirable for large scale synthesis because of the largeamounts of water required. In addition, the amount of nickel in the LiNMC composition is undesirably low for most commercial applications.

[0054] 2020 Hua, Chemistry of Materials, 32 (2020) 4984-4997 heated a co- precipitated hydroxide of compositions (Ni0.33Mn0.33Co0.33)(OH)2and (Ni0.6Mn0.2Co0.2)(OH)2 in an oxygen containing atmosphere. In both cases, this resulted in the formation of a two-phase metal oxide cubic spinel and metal oxide rock-salt mixture. For the (Ni0.33Mn0.33Co0.33)(OH)2 composition it was noted that the cubic spinel phase and the rock-salt phase do not have an even distribution of Ni, Co, and Mn. For the (Ni0.6Mn0.2Co0.2)(OH)2 composition it was noted that the two phase nature of the product is likely to result in segregation of the transition metal ions, that is, the two phases contain different amounts of Ni, Co, and Mn ions. Both products were heated in an oxygen containing atmosphere to produce LiNMC. However, the method utilized a co- precipitation, which is not desirable for large scale synthesis because of the large amounts of water required.

[0055] Dry method steps have been described in the process steps for making LiNMC. 2020 Lituo et al., Journal of The Electrochemical Society, 167 (2020) describes dry method steps for making LiNMC that utilizes a rock-salt precursor oxide phase having the formula (NinMnmCoc)1-aAaLibO1+b. The rock-salt precursor oxide is then lithiated by heating in air with a lithium source (such as Li2CO3or LiOH) to produce LiNMC, including SC-LiNMC. However, ball milling is used to ensure an atomically homogeneous distribution of metals and dopants in the precursor. In this process, ball milling may introduce contamination from the milling media. Additionally, a second nickel source was not added after a first sintering.

[0056] Thus, some embodiments herein disclose an all-dry process for the production of cubic spinel phase NMC precursor particulates. Some embodiments herein comprise a method that includes: a) obtaining feedstock components that include a nickel source, a manganese source, and a cobalt source; b) combining the feedstock components according to a feedstock combining procedure to produce a feedstock mixture; c) heating the feedstock mixture in an oxygen containing atmosphere at a temperature greater than about 450°C according to a feedstock mixture heating procedure to obtain a precursor particulate comprising a precursor spinel phase; d) obtaining precursor components that include the precursor particulate, a lithium source, a second nickel source, and, optionally, a second cobalt source; e) combining the precursor components according to a precursor particulate combining procedure to produce a precursor mixture; and f) heating theprecursor mixture in an oxygen containing atmosphere at a temperature greater than about 700°C according to a precursor mixture heating procedure to obtain a product LiNMC.

[0057] In some embodiments a nickel manganese cobalt oxide precursor particulate having a majority phase of cubic spinel oxide is produced according to the process of: a) obtaining feedstock components that include a nickel source, a manganese source, and a cobalt source; b) dry mixing the feedstock components to obtain a feedstock mixture, wherein the molar amount of Ni in the feedstock mixture is about 47% or less than of the molar amounts of manganese and cobalt individually; c) heating the feedstock mixture an oxygen containing atmosphere from a temperature below about 50°C to an elevated temperature between about 700°C to about 1200°C and holding at the elevated temperature for at least an hour; and d) cooling the feedstock mixture to a temperature below about 100°C to obtain the nickel manganese cobalt oxide precursor particulate having a majority phase of cubic spinel oxide.

[0058] Figure 17 is a flow chart for preparing a lithium nickel manganese cobalt oxide cathode material according to some embodiments herein. At step 1710, the process includes obtaining feedstock components that include a nickel source, a manganese source, and a cobalt source. At step 1720, the process includes combining the feedstock components in a feedstock component Ni:Mn:Co:A molar ratio. At step 1730, the process includes heating the feedstock mixture in an oxygen containing atmosphere to a temperature greater than about 450°C according to a feedstock mixture heating procedure to obtain a precursor particulate. At step 1740, the process includes combining precursor components that include the precursor particulate, a lithium source, and a second nickel source to obtain a precursor mixture. At step 1750, the process includes heating the precursor mixture in an oxygen containing atmosphere at a temperature greater than about 700°C to obtain the lithium nickel manganese cobalt oxide cathode material.

[0059] In preferred embodiments the feedstock components are in the form of powders. In such embodiments it has been observed that the small particle size aids in the solid-state reaction of these components during the feedstock mixture heating procedure. Therefore, in preferred embodiments the feedstock components are in the form of powders with a particle size less than about 100 μm or, more preferably, less than about 50 μm, less than about 10 μm, or even smaller. In some embodiments the feedstock components are in the form of powders with a particle size in the range of about 0.01 μm to about 0.1 μm, about 0.1 μm to about 5 μm, about 1 μm to about 10 μm, about 10 μm to about 50 μm, orabout 50 μm to about 100 μm. In one embodiment the powder particle size is smaller than 10 μm to increase the homogeneity of the feedstock mixture.

[0060] In some embodiments the nickel source is a nickel containing oxide, a nickel containing hydroxide, a nickel containing carbonate, nickel metal, a nickel containing alloy, or mixtures thereof; the manganese source is a manganese containing oxide, a manganese containing hydroxide, a manganese containing carbonate, manganese metal, a manganese containing alloy; or mixtures thereof; and the cobalt source is a cobalt containing oxide, a cobalt containing hydroxide, a cobalt containing carbonate, cobalt metal, a cobalt containing alloy; or mixtures thereof. In some embodiments of heating in the presence of oxygen, if a metal or alloy is used as a nickel source, manganese source or a cobalt source, the metals will oxidize during the feedstock mixture heating procedure to produce oxides. Specific examples of suitable nickel sources include NiO, Ni(OH)2, and nickel metal. Specific examples of suitable manganese sources include MnO2, Mn2O3, Mn3O4, MnO, Mn(OH)2, MnCO3, and manganese metal. Specific examples of suitable cobalt sources include Co3O4, CoO, Co(OH)2, CoCO3, and cobalt metal.

[0061] In the present invention, the feedstock components consist at least of a nickel source, a manganese source, and a cobalt source. In some embodiments the feedstock components further contain one or more dopant element sources. Suitable dopant elements sources are oxides, hydroxides or carbonates of the dopant element A. The dopant element A in its elemental form may also be used as a suitable dopant element source. Examples of suitable dopant element sources include, Al, Ti, Zr, Zn, Fe, Mo, K, Na, Si, Ta, B, Nb, W, and mixtures thereof. Suitable dopant element sources may be selected from the group consisting of metals, metal oxides, metal hydroxides, metal carbonates and mixtures thereof. In particular, dopant element sources can be Fe, Mo, Si, Ta, B, Nb, W, MgO, Al2O3, TiO, TiO2, ZrO2, ZnO, FeO, Fe2O3, Fe3O4, MoO3, K2O, Na2O, SiO2, Ta2O5, Mg(OH)2, Al(OH)3, AlO(OH), Zr(OH)4, Zn(OH)2, Fe(OH)2, FeO(OH), Fe(OH)3, KOH, B2O3, WO3, Nb2O5, or NaOH.

[0062] In some embodiments the feedstock components can include a flux which may enhance the diffusion of transition metals during the feedstock mixture heating procedure or the precursor mixture heating procedure, resulting in greater compositional homogeneity and improved crystallinity and morphology of the product LiNMC. Suitable fluxes are materials that are molten during the heating procedures, are materials in which oxides of nickel, manganese, and cobalt have some solubility, and are materials whose components do not substantially incorporate into the precursor spinel phase (other thanoxygen) or do not substantially incorporate in the LiNMC phase in the product LiNMC. Examples of suitable fluxes include alkali metal sulfate salts, such as Li2SO4, Na2SO4, K2SO4 and combinations thereof. Suitable fluxes can also include oxides, such as B2O3, WO3, BiO2, and MoO3. In some embodiments, salts which additionally are soluble in water can be particularly useful, since such fluxes may be removed by washing with water. In some embodiments the flux may coat the product LiNMC, while still remaining a separate phase from the LiNMC phase. In some instances, the flux may remain as a separate phase in the product LiNMC and provide additional benefits related to the product LiNMC electrochemical performance. BiO2 and WO3 are particularly useful in this regard. During the precursor mixture heating procedure these fluxes may react to form new products. For instance, WO3 is known to react during the precursor mixture heating procedure to form a Li4+xM1−xWO6type phases, where M can include Ni, Mn or Co, that reside on the surfaces of LiNMC grains in the product LiNMC.

[0063] The feedstock combining procedure can comprise the steps of selecting an appropriate feedstock combining apparatus and a process for the feedstock combining apparatus, adding the feedstock components to the combining apparatus in amounts such that the added feedstock components have a Ni:Mn:Co:A molar ratio (the feedstock component Ni:Mn:Co:A molar ratio) where the feedstock component Ni:Mn:Co:A molar ratio is equal to the Ni:Mn:Co:A molar ratio of the desired precursor particulate (the precursor particulate Ni:Mn:Co:A molar ratio) and then triturating the amounts of feedstock components according to said process.

[0064] In some embodiments the feedstock component Ni:Mn:Co:A molar ratio is x:y:z:w where x + y + z = 1, x ≥ 0, 0.10 ≤ y ≤ 0.90, z ≥ 0, and 0 ≤ w ≤ 0.05.

[0065] In some embodiments the feedstock component Ni:Mn:Co:A molar ratio is x:y:z:w where x + y + z = 1, x ≥ 0, 0.10 ≤ y ≤ 0.90, z ≥ 0.05, and 0 ≤ w ≤ 0.05.

[0066] In some embodiments the Ni is about 47% or less of either of the molar amounts of manganese or cobalt that are mixed in the feedstock mixture. In some embodiments Ni is about 40% or less, about 35% or less, about 30% or less, about 25% or less, about 20% or less, about 15% or less, or about 10% or less than either of the molar amounts of manganese or cobalt in the feedstock mixture. In some embodiments the amount of Ni may be between any of these ranges (e.g., about 15-20%, about 20-25%, etc.).

[0067] In some embodiments the feedstock component Ni:Mn:Co:A molar ratio is x:y:z:w, where x + y + z = 1, 0 ≤ w ≤ 0.05, and where the Ni, Mn, and Co composition is within the region “R” in Figure 2. That is, the Ni, Mn, and Co composition is defined tobe within the region of the Ni-Mn-Co ternary composition diagram bounded by the line segments ακ, κν, νδ, δε, εξ, and ξα where: α = Mn0.2Co0.8 κ = Mn0.8Co0.2ν = Ni0.2Mn0.8 δ = Ni0.47Mn0.53ε = Ni0.47Mn0.36Co0.17 ξ = Ni0.8Co0.2

[0068] In some embodiments the feedstock component Ni:Mn:Co:A molar ratio is x:y:z:w, where x + y + z = 1, 0 ≤ w ≤ 0.05, and where the Ni, Mn, and Co composition is within the region “S” in Figure 3. That is, the Ni, Mn, and Co composition is defined to be within the region of the Ni-Mn-Co ternary composition diagram bounded by the line segments αβ, βγ, γδ, δε, εζ, ζη, and ηα where: α = Mn0.2Co0.8β = Mn0.5Co0.5 γ = Ni0.25Mn0.75 δ = Ni0.47Mn0.53 ε = Ni0.47Mn0.36Co0.17 ζ = Ni0.30Mn0.36Co0.34η = Ni0.1Mn0.1Co0.8

[0069] In some embodiments the feedstock component Ni:Mn:Co:A molar ratio is x:y:z:w, where x + y + z = 1, 0 ≤ w ≤ 0.05, and where the Ni, Mn, and Co composition is within the region “T” in Figure 4. That is, the Ni, Mn, and Co composition is defined to be within the region of the Ni-Mn-Co ternary composition diagram bounded by the line segments σβ, βγ, γτ, and τσ where: σ = Mn0.3Co0.7 β = Mn0.5Co0.5γ = Ni0.25Mn0.75 τ = Ni0.40Mn0.60

[0070] The feedstock combining procedure can include mixing or blending processes or means for mixing or blending utilizing mixers or blenders as the feedstock apparatus. Examples of suitable mixers or blenders include a paddle mixer, high shear mixer, shaker mixer, ribbon mixer, plough mixer, collette mixer, twin-screw mixer / kneader, a Loedige mixer, a Julia mixer, or a V-blender. The feedstock combiningprocedure can also include trituration processes utilizing triturators, mills or grinders as the feedstock apparatus. Suitable trituration processes may be either “wet” or “dry”. Desirably, however, dry processes are used. Suitable triturators, mills or grinders include an automatic grinder or mortar and pestle as used in the following Examples. However, for commercial purposes, larger scale apparatus for jet milling, ball milling, bead milling, small media milling, agitator ball milling, planetary milling, horizontal ball milling, pebble milling, rod milling, attritor milling, pulverizing, hammer milling, and the like would be more suitable. In some embodiments the trituration apparatus is configured such that it has non-metallic mixing components to prevent contamination of the precursor particulate. In some embodiments these non-metallic components are ceramic, ceramic-glass, composite, reinforced composite, or other hard non-metallic materials. In some embodiments the feedstock components do not react during the feedstock combining procedure. In some embodiments the feedstock components react during the feedstock combining procedure to form new phases. In some embodiments the feedstock combining procedure results in a reduction of the particle size of some or all of the feedstock components. In some embodiments the feedstock combining procedure results in a reduction of the grain size of some or all of the feedstock components. Suitable feedstock combining procedures result in a homogeneous distribution of the feedstock components. In particular, the arrangement of feedstock component phases in the feedstock mixture should be random on a scale less than 200 μm, less than 100 μm or more preferably less than 50 μm, less than 10 μm or even smaller. In some embodiments the feedstock component phases are in a range of about 0.1 μm to about 10 μm, about 10 μm to about 50 μm, about 50 μm to about 100 μm, or about 100 μm to about 200 μm.

[0071] In some embodiments the combining, mixing, or trituration of the feedstock mixture or the precursor mixture is a dry process. In some embodiments the mixing is an all-dry or solid-state mixing that facilitates mixing on the atomic level. In some embodiments the mixing is substantially free of solvents or solvent residues. Advantageously, the dry mixing enables the conservation of water and energy.

[0072] In various embodiments a feedstock mixture containing a nickel source, a manganese source, and a cobalt source is heated at temperatures exceeding 450 degrees Celsius to obtain a precursor particulate, and lithium and a second nickel source are added to the precursor particulate to obtain a precursor mixture. In some embodiments the Ni:Mn:Co:A molar ratio in the feedstock mixture is different than the Ni:Mn:Co:A molar ratio in the precursor mixture. In some embodiments the Ni:(Mn+Co+A) molar ratio in thefeedstock mixture is at least 5% different than the Ni:(Mn+Co+A) molar ratio in the precursor mixture. In some embodiments the Ni:(Mn+Co+A) molar ratio in the feedstock mixture is at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50% different, at least about 70% different than the Ni:(Mn+Co+A) molar ratio in the precursor mixture. In some embodiments the difference may be a percentage between these percentages (i.e. 10-20%). In some embodiments the Ni:(Mn+Co+A) molar ratio in the feedstock mixture is about 1 / 10 of the Ni:(Mn+Co+A) molar ratio in the precursor mixture, about 1 / 8 of the Ni:(Mn+Co+A) molar ratio in the precursor mixture, about 1 / 7 of the Ni:(Mn+Co+A) molar ratio in the precursor mixture, about 1 / 5 of the Ni:(Mn+Co+A) molar ratio in the precursor mixture, about 1 / 3 of the Ni:(Mn+Co+A) molar ratio in the precursor mixture, about 1 / 2 of the Ni:(Mn+Co+A) molar ratio in the precursor mixture, or any value between these ratios. In some embodiments the Ni:(Mn+Co+A) molar ratio in the feedstock mixture is zero and the Ni:(Mn+Co+A) molar ratio in the precursor mixture is greater than or equal to 0.5.

[0073] The feedstock mixture heating procedure can include heating the feedstock mixture in an oxygen containing atmosphere at a heating temperature that causes a nickel source, a manganese source, and a cobalt source to react to form a precursor particulate comprising a precursor spinel phase. The feedstock mixture heating procedure may be any of the heating processes disclosed in the examples herein. Heating temperatures can include those that are greater than about 450°C. Heating temperatures greater than about 700°C are particularly advantageous, since they reduce the reaction time. The heating temperature should not be too high, for instance greater than about 1600°C, as the precursor spinel phase may decompose at such temperatures. However, a high temperature step may be included, if a lower temperature heating step or a slow cooling step follows in which the sample may regain a precursor spinel phase. As a particular example, about 900°C may be a suitable heating temperature. The time the feedstock mixture spends at the heating temperature can be determined by measuring the x-ray powder diffraction pattern of the feedstock mixture at different times during the heating process. The heating time should be maintained until a precursor particulate comprising a precursor spinel phase is formed. Additional heating time of 30 minutes to 20 hours beyond the initial formation of this phase is used to ensure a complete reaction of the feedstock components and improve a precursor particulate homogeneity. As particular examples, 2 hours, 4 hours, 8 hours, 12 hours, or 24 hours may be suitable heating times at a about 900°C heating temperature.

[0074] Oxygen containing atmospheres used in the feedstock mixture heating procedure should be selected such that the oxygen partial pressure is sufficient for the precursor spinel phase to form and such that oxygen is the only element from the oxygen containing atmosphere that is substantially incorporated in the precursor particulate composition. Examples of oxygen containing atmospheres suitable for the feedstock mixture heating procedure include O2(g), air, or mixtures of oxygen with other gases, including inert gases, such as N2(g), Ar(g), and other oxygen containing gases, such as CO2.

[0075] A precursor spinel phase is a nickel, manganese, and cobalt containing oxide having a spinel structure. In some embodiments the precursor spinel phase has a cubic spinel structure (such as shown in Figure 16). The precursor particulate can further contain a dopant element A. The dopant element A may be incorporated into the precursor spinel phase or it may reside in a different phase. In some embodiments the precursor particulate can contain a rock-salt phase oxide (such as shown in Figure 15), including a Ni-containing rock-salt phase oxide. However, it has been found that improved compositional homogeneity can be achieved in the product LiNMC if the precursor particulate consists essentially of a precursor spinel phase. Therefore, in the most preferred embodiment, the precursor particulate consists essentially of a precursor spinel phase. Examples of precursor spinel phases that are cubic spinels include (Ni0.070Mn0.465Co0.465)3O4and (Ni0.090Mn0.455Co0.455)3O4.

[0076] In preferred embodiments the precursor components are in the form of powders. In such embodiments it has been observed that the small particle size aids in the all-dry or solid-state reaction of these components during the precursor mixture heating procedure. Therefore, in preferred embodiments the precursor components are in the form of powders with a particle size less than about 100 μm or, more preferably, less than about 50 μm, less than about 10 μm, or even smaller or in a range of about 0.01 μm to about 0.1 μm, about 0.1 μm to about 5 μm, about 5 μm to about 10 μm, or about 10 μm to about 100 μm. To achieve such sizes, grinding steps may be employed to reduce the particle size of each precursor component individually.

[0077] The lithium source used can be lithium carbonate, lithium hydroxide or lithium oxide or mixtures thereof. In some embodiments the precursor components include a second nickel source or a second cobalt source. Examples of suitable second nickel sources include a nickel containing oxide, a nickel containing hydroxide, a nickel containing carbonate, nickel metal, a nickel containing alloy, or mixtures thereof. Examples of suitable second cobalt sources include a cobalt containing oxide, a cobaltcontaining hydroxide, a cobalt containing carbonate, cobalt metal, a cobalt containing alloy; or mixtures thereof. In some embodiments the precursor components may include a flux.

[0078] In some embodiments the precursor combining procedure or combining the precursor components comprises the steps of selecting an appropriate precursor combining apparatus and then combining appropriate amounts of the precursor components (including a precursor particulate, a second nickel source, a lithium source, and optionally a second cobalt source) according to said process. The amount of lithium source used in the precursor particulate combining procedure can be between about 0 to about 30% greater than the stoichiometric amount required to make the product LiNMC. The amounts of precursor particulate, second nickel source, and second cobalt source used in the precursor particulate combining procedure can be the stoichiometric amounts required to make the product LiNMC.

[0079] In some embodiments the precursor combining procedure or combining precursor components can include mixing or blending processes utilizing mixers or blenders as the precursor mixing apparatus. Examples of suitable mixers or blenders include a paddle mixer, high shear mixer, shaker mixer, a Loedige mixer, a Julia mixer, or a V-blender. The precursor combining procedure can also include trituration processes utilizing triturators, mills or grinders as the precursor mixing apparatus. Trituration may be performed in a wet or dry manner, but the methods disclosed herein advantageously allow for dry trituration absent of solvents and / or solvent residues. Suitable triturators, mills, or grinders include an automatic grinder or mortar and pestle as used in the following examples. However, for commercial purposes, larger scale apparatus for jet milling, ball milling, bead milling, small media milling, agitator ball milling, planetary milling, horizontal ball milling, pebble milling, rod milling, attritor milling, pulverizing, hammer milling, and the like may be more suitable. In some embodiments the precursor components do not react during the precursor combining procedure. In some embodiments the precursor components react during the precursor combining procedure to form new phases. In some embodiments the precursor combining procedure results in a reduction of the particle size of some or all of the precursor components. In some embodiments the precursor combining procedure results in a reduction of the grain size of some or all of the precursor components. Suitable precursor combining procedures result in a homogeneous distribution of the precursor components. In particular, the arrangement of precursor component phases in theprecursor mixture should be random on a scale less than about 200 μm, less than about 100 μm or more preferably less than about 50 μm, less than about 10 μm or even smaller.

[0080] The precursor mixture heating procedure includes heating the precursor mixture in an oxygen containing atmosphere at a heating temperature that causes the lithium source, precursor particulate, and, where present, the second nickel source to react to form LiNMC. Suitable heating temperatures include those that are greater than about 600°C. Heating temperatures greater than about 700°C are particularly useful, since they reduce the reaction time. The heating temperature should not be too high, for instance greater than about 1600°C, as LiNMC may decompose at such temperatures. However, a high temperature step may be included, if a lower temperature heating step or a slow cooling step follows, in which the sample may reform as LiNMC. As a particular example, about 900°C may be a suitable heating temperature. The time the precursor mixture spends at the heating temperature can be determined by measuring the x-ray powder diffraction pattern of the precursor mixture at different times during the heating process and observing the LiNMC particle morphology by electron microscopy. The heating time should be maintained until the desired LiNMC crystal structure and particle morphology are obtained. In some embodiments additional heating time of 30 minutes to 20 hours beyond the initial formation of the LiNMC phase is used to ensure a complete reaction of the precursor components, and improve LiNMC homogeneity, crystal structure, and particle morphology. As particular examples, 2 hours, 4 hours, 8 hours, 12 hours, or 24 hours may be suitable heating times at a about 900°C heating temperature.

[0081] Oxygen containing atmospheres used in the precursor mixture heating procedure should be selected such that the oxygen partial pressure is sufficient for the LiNMC phase to form and that oxygen is the only element from the oxygen containing atmosphere that is substantially incorporated in the LiNMC composition. Examples of oxygen containing atmospheres suitable for the precursor mixture heating procedure include O2(g), air, or mixtures of oxygen with other gases, including inert gases, such as N2(g), Ar(g), and other oxygen containing gases, such as CO2.

[0082] In some embodiments a LiNMC product produced according to some methods herein contains a LiNMC phase having an O3 layered structure and the formula Li1+p[(NinMnmCoc)1-aAa]1-pO2, where -0.03 ≤ p ≤ 0.06; n + m + c = 1; n ≥ 0.50; m ≥ 0.05; c ≥ 0; A is a metal dopant; and 0 ≤ a ≤ 0.05. In some embodiments, the product LiNMC contains a LiNMC phase having an O3 layered structure and have the general formulaLi1+p[(NinMnmCoc)1-aAa]1-pO2, where -0.03 ≤ p ≤ 0.06; n + m + c = 1; n ≥ 0.50; m ≥ 0.05; c ≥ 0.05; A is a metal dopant; and 0 ≤ a ≤ 0.05.

[0083] The product LiNMC may have different morphologies, depending on the heating temperature and heating time used in the precursor mixture heating procedure. In preferred embodiments the product LiNMC is in the form of a powder. If the heating temperature used in the precursor mixture heating procedure is lower than about 900°C, the LiNMC can be in the form of a powder consisting mainly of polycrystalline secondary particles with the primary particles less than about 1 μm in size. If the heating temperature used in the precursor mixture heating procedure is greater than about 900°C and the heating time used is greater than one hour, the LiNMC can be in the form of a powder consisting of primary particles that are greater than about 1 μm in size. In some embodiments, the LiNMC product comprises SC-LiNMC. In some embodiments, the LiNMC product comprises SC-LiNMC particles in which essentially each particle consists of multiple LiNMC grains. In preferred embodiments, the LiNMC product comprises SC-LiNMC particles in which essentially each particle consists of a single LiNMC grain. In some embodiments the product LiNMC has an average particle size (D50) between about 0.1 μm and about 20 μm. In more preferred embodiments the product LiNMC has an average particle size (D50) is between about 2 μm and about 10 μm.

[0084] The product LiNMC can additionally contain other phases. Phases that form a coating around the LiNMC phase grains are particularly advantageous. Such phases include lithiated oxides of tungsten, bismuth, and zirconium. However, to achieve high energy densities when used in a Li-ion cell, the product LiNMC should be greater than about 90% by weight LiNMC phase. In preferred embodiments, the product LiNMC is greater than about 95% by weight LiNMC phase, greater than about 98% by weight LiNMC phase, or greater than about 99% by weight LiNMC phase. In some embodiments the product LiNMC essentially consists of LiNMC phase.

[0085] Additional post-processing steps may be applied to the product LiNMC cathode material. Deagglomeration processes, such as those in which secondary product LiNMC particles are deagglomerated, can be used. They can include those processes in which product LiNMC particles are deagglomerated into SC-LiNMC in which essentially each particle consists of a single LiNMC grain. Jet milling is a preferred example of such a deagglomeration process. Other examples include ball milling, bead milling, small media milling, agitator ball milling, planetary milling, horizontal ball milling, pebble milling, rod milling, or attritor milling. These may be wet or dry milling processes, but advantageouslythese can be dry processes to enable an all-dry method of synthesizing a SC-LiNMC. An additional refiring (second firing) may be conducted as a post-processing step after deagglomeration to reduce lithium residuals on the SC-LiNMC. Other additional processing steps can be performed including washing the product LiNMC cathode material with a suitable solvent to remove surface lithium containing species. Suitable solvents include water and ethanol. However, in some instances the deagglomeration or washing process can cause defects in the LiNMC crystal structure. Therefore an additional heating step may be implemented after the deagglomeration process to remove such defects. A lithium source may be included in this heating step. Other additional processing steps can include the application of coatings on the surface of the product LiNMC particles. Examples of useful coatings include Al2O3, ZrO2, and TiO2.

[0086] The methods for examples disclosed herein were performed at standard temperature and pressure, unless otherwise indicated.

[0087] As shown with reference to examples below, the feedstock component Ni:Mn:Co:A molar ratio is correlated with the crystal structure of the precursor particulate and the types of phases that are present in the precursor particulate, such as cubic spinel, tetragonal spinel, or rock-salt phase. By using predetermined Ni:Mn:Co:A molar ratios in the feedstock mixture, the precursor particulate will form having a cubic spinel oxide majority phase and have a Ni:Mn:Co ratio that falls within the region of the Ni-Mn-Co ternary composition diagram bounded by the line segments ακ, κν, νδ, δε, εξ, and ξα where α = Mn0.2Co0.8, κ = Mn0.8Co0.2, ν = Ni0.2Mn0.8, δ = Ni0.47Mn0.53, ε = Ni0.47Mn0.36Co0.17, and ξ = Ni0.8Co0.2. In some embodiments the predetermined molar ratios of the Ni:Mn:Co:A feedstock mixture will produce a precursor particulate consisting essentially of a cubic spinel oxide structure whose Ni, Mn, and Co content falls within the region of the Ni-Mn- Co ternary composition diagram bounded by the line segments σβ, βγ, γτ, and τσ where σ = Mn0.3Co0.7, β = Mn0.5Co0.5, γ = Ni0.25Mn0.75, τ = Ni0.40Mn0.60. A precursor particulate being in the form of an oxide with a cubic spinel structure is desirable as this indicates that the NMC feedstock materials are sufficiently mixed on an atomic scale, which has generally only been feasible with a co-precipitation process. Counterintuitively, in embodiments herein the feedstock component Ni:Mn:Co molar ratio is not the same as or substantially the same as the Ni:Mn:Co molar ratio in the final NMC cathode material. In some embodiments the Ni:(Mn+Co) ratio in the feedstock component mixture is not the same as or substantially the same as the Ni:(Mn+Co) molar ratio in the final NMC cathode material. In some embodiments the Ni:Mn:Co molar ratio in the precursor particulate is not the sameas or substantially the same as the Ni:Mn:Co molar ratio in the final NMC cathode material. In some embodiments the Ni:(Mn+Co) ratio in the precursor particulate is not the same as or substantially the same as the Ni:(Mn+Co) molar ratio in the final NMC cathode material. In each of the aforementioned ratios an optional dopant (A) may be included, which may be same or different in the feedstock particulate as in the final NMC cathode material. In some embodiments herein all of the Mn and optional dopant (A) are provided in the feedstock mixture and only some of the Ni and Co are provided in the feedstock mixture, and additional Ni and Co are provided in a subsequent mixing step after a firing of the feedstock mixture. In some embodiments, all of the Mn, Co, and optional dopant are provided in their stoichiometric amounts in the feedstock mixture and only some of the stoichiometric amount of Ni is provided in the feedstock mixture prior to a first firing of the feedstock mixture in excess of 700 Celsius. As a non-limiting example, in the case of NMC622 (LiNi0.6Mn0.2Co0.2O2) all of the stoichiometric amount of Mn and Co are provided (molar amount of 0.2) in the feedstock mixture, but only a portion of the Ni (for example ~33% of the 0.6 molar amount) is provided in the feedstock mixture prior to a firing of the feedstock mixture in excess of 700 Celsius. After the firing of the feedstock mixture the remaining stoichiometric amount of Ni (for example ~66% of the 0.6 molar amount) is added to provide the final stoichiometric amount of Ni. Providing Ni in a piecewise manner allows a more homogeneous dry mixing (equivalent to the homogeneous mixing done via co-precipitation), which is generally shown by the creation of particles having a cubic spinel oxide phase as the majority phase after the firing of the feedstock mixture.

[0088] Figure 15 shows an exemplary polyhedral representation of a cubic rock-salt crystal structure where the corners of the octahedra represent the locations of anions and the center of the octahedra represent the locations of cations. As depicted, the cubic rock-salt crystal structure is absent of cation layering order.

[0089] Figure 16 shows an exemplary polyhedral representation of the cubic spinel crystal structure of the general formula DE2X4where the corners of the octahedra and tetrahedra represent the locations of X anions, the center of the octahedra represent the locations of the E cations, and the center of the tetrahedra represent the location of the D cations. The polyhedral representation in Figure 16 illustrates a cation such as lithium (lightly shaded) in a cation layering order. However, a precursor particulate cubic spinel crystal that is formed may be absent lithium ions where the precursor particulate is formed without the addition of lithium, such as with the mixing of NiO, Mn3O4, and Co3O4.

[0090] In some aspects the disclosure relates to a battery containing the lithium nickel manganese cobalt 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 storage devices, electric tools, electric bicycles, electric toys, or any other electrically-powered device. Definitions

[0091] As used herein, 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.

[0092] In a related manner herein, the phrase “essentially the same” is to be interpreted as meaning “the same as” but also to include – and not to exclude – any items or steps that do not materially affect the basic characteristics of the items or steps involved.

[0093] The term “triturating” herein 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 process comprising both comminuting and blending.

[0094] The term “stoichiometric” herein 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 the ratio of reactants in a chemical equation or formula. For example, H2O refers to a ratio of two hydrogen atoms for every one oxygen atom in the water molecule and may be produced according to the stoichiometric equation 2H + O → H2O. Stoichiometric values may be whole numbers or integers, or they may be fractions that could be multiplied by a number such that they are whole numbers or integers.

[0095] The term “stoichiometry” should be given its ordinary meaning as it would be understood by a person having ordinary skill in the art but often refers to the molar ratio of components. For example, NMC811 has a stoichiometry written as LiNi0.8Mn0.1Co0.1O2 and NMC622 has a stoichiometric ratio written as LiNi0.6Mn0.2Co0.2O2.

[0096] The word “molar amount” used herein is intended to refer to the final desired amount of a component in the cathode product as measured in moles.

[0097] The term “molar ratio” herein 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 the ratio between the amounts in moles of any two compounds. A mole of a substance is equivalent to 6.02214076 x1023elementary entities (e.g., atoms, molecules) of that substance.

[0098] “Metal 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 invention but often refers to the group of metals capable of serving as a dopant in a lithium transition metal oxide and includes the metals Mg, Al, Ti, Zr, W, Zn, Mo, K, Na, Si, Ta, B, Nb, W, and mixtures thereof but excludes the metals Ni, Mn, and Co.

[0099] In a quantitative context, the term “about” should be construed according to 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 includes the range up to plus 1% and down to minus 1%.

[0100] The term “grain” 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 crystallite, the terms being used interchangeably herein.

[0101] “Particulate” 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 plurality of “particles” in which the “particles” are composed of one or more grains.

[0102] Unless the context requires otherwise, throughout this specification and claims, the words “comprise”, “comprising” and the like are to be construed in an open, inclusive sense. The words “a”, “an”, and the like are to be considered as meaning at least one and are not limited to just one.

[0103] 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 provided in the alternative (“or”).

[0104] As used herein, “transition metals” refer to elements in columns 3-12, rows 4-6 of the periodic table. Some examples of transition metals are Mn, Ni, and Co. A transition metal stoichiometry is intended to refer a proportion of one or more transition metals in a material.

[0105] The term “dry” or “liquid-free environment” should be given its ordinary meaning as it would be understood by a person having ordinary skill in the art atthe time of the disclosure but often refers to an environment that is free or substantially free of solvents including organic or aqueous solvents prior to the heating and melting of the materials.

[0106] The term “all-dry” 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 an entire process that is substantially free of solvents, including water or organic solvents. All-dry includes a series of solid-state steps that are free of added liquids or solvents.

[0107] The term “solvent residues” 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 residues from salts, acids, bases, trace metals, or trace impurities. Trace metals may include sodium, magnesium, calcium, iron, etc. Trace impurities may comprise residues incompletely removed from solvent reagents. These trace impurities may be present because they are acceptable according to industry standards for the purity of certain reagents. These trace impurities may be in amounts of parts per million (ppm) or parts per billion (ppb).

[0108] The term “solid-state” 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 reaction that is free of solvents. The reaction does not need to be mediated by solvents, including water or organic solvents.

[0109] “Single crystal morphologies” or “single crystal” 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 generally refers to refers to a crystalline solid where the particle consists essentially of one or more grains, where the average grain facet size is greater than 20% of the average particle size. In some embodiments of single crystal particles, each particle consists of a single crystal essentially free from interparticle boundaries.

[0110] The term “cathode” should be given its ordinary meaning as it would be understood by a person having skill in the art at the time of the disclosure and refers to the electrode at which reduction occurs when a metal-ion battery is discharged. In a lithium- ion cell, the cathode is the electrode that is lithiated during discharge and delithiated during charge. The cathode may also be called the “positive electrode.” Cathode materials such as NMC, LCO, LMO, and NCA may be termed “active materials of the positive electrode” or “active cathode materials.”

[0111] The term “D50” 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 the median particle size of a group of particles, as measured by a random group of particles.

[0112] The term “average particle size” 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 the average of the greatest dimension of at least 20 random particles as observed through a laser particle size analyzer or by electron microscopy.

[0113] The term “Ni-Mn-Co ternary composition diagram” 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 mapping of just the Ni, Mn, and Co content of a particular composition. This mapping does not map out the oxygen content in the composition.

[0114] The term “rock-salt phase” 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 rock-salt crystal structure that is absent of cation layering order.

[0115] The term “cubic spinel phase” 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 (MgAl2O4), 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 in half of the octahedral sites formed by the anion lattice. A substance having cubic spinel structure may also be described as a crystal structure having the general formula DE2X4and 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. Examples

[0116] Cell Preparation and Testing

[0117] Electrochemical analysis was done using coin-configuration half-cells. Polyvinylidene fluoride (PVDF, MW=534k, Sigma-Aldrich) was fully dissolved in N- Methyl-2-pyrrolidone (NMP, Sigma-Aldrich) (overnight), and then Super C65 carbonblack (Imerys) was added and mixed with a high-shear mixer for 1h for dispersion. Active material (e.g., NMC active material) was added to this slurry for a final ratio of 80:12:8%wt active:C65:PVDF ratio, and 37%wt total solids in the slurry. For dispersion and deagglomeration, 5.3g of this slurry was mixed in a planetary ball-mill (Retsch PM200), in a 50ml tungsten carbide vial, with 3 tungsten carbide balls (d=12mm) at 100rpm for 2h. The final slurry was applied to an aluminum foil at 6 / 1000” thickness and dried at 120°C under active vacuum overnight.

[0118] Cell assembly was done in an argon-filled glovebox. The counter / reference electrode was Lithium metal (Sigma-Aldrich). Coin-cell geometry was CR2325. 0.03” spacers were attached to each electrode (cathode – aluminum, anode – copper) with no wave spring. A sheet of blown polypropylene microfibers (3M) and a sheet of trilayer porous polypropylene-polyethylene-polypropylene (Celgard 2325) separators were used, with the trilayer separator on the lithium side. The electrolyte solution was 1M lithium hexafluorophosphate in ethylene carbonate : diethyl carbonate : fluoroethylene carbonate 3:6:1vol (BASF), added to the cell in large excess.

[0119] Cell cycling was done in a Maccor Series 4000 system (Maccor) at 30°C. The first cycle was done at C / 20 rate and all following cycles at C / 5, in the voltage range 2.5—4.3V. C-rate was calculated from active material weight assuming 180mAh / g initial capacity. In all cycles, at the end of cathode delithiation (charge), constant 4.3V voltage was maintained until current dropped to half of cycle rate (C / 40 or C / 10). Specific capacity is reported in terms of active powder mass (rather than full electrode mass).

[0120] Examples 1—8

[0121] Precursor particulates having different Ni:Mn:Co molar ratios of x:y:z as listed in Table 1, were prepared by triturating the following feedstock components: NiO (≥78.5% Ni content, -400 mesh, Thermo Scientific), Mn3O4 (97%, Sigma Aldrich), and Co3O4(99.7%, -400mesh, Alfa Aesar) according to the amounts listed in Table 1 by using an automatic mortar grinder (Retsch RMO) for 4h to make feedstock mixtures. The resulting feedstock mixtures were then placed in an alumina crucible and heated in a tube furnace in air from ambient temperature at rate 5°C / min to 900°C, held isothermally for 4h, and then the furnace was allowed to naturally cool to below 100°C. The resulting precursor particulate was then ground by mortar and pestle.

[0122] Figure 5 shows the XRD patterns of the precursor particulates of Examples 1-8. In the figure circles indicate XRD peaks from cubic spinel phases, trianglesindicate peaks from tetragonal spinel phases, and squares indicate peaks from rock salt phases. The phases present in these samples as identified by x-ray diffraction are listed in Table 1. The precursor particulates of Examples 1-7 have XRD patterns consistent with a cubic spinel oxide phase being the majority phase in the sample. In addition to the cubic spinel oxide phase, the precursor particulate of Example 1 is a multi-phase particulate and contains a rock-salt phase and a tetragonal spinel phase. The precursor particulates of Examples 2 and 3 are phase pure cubic spinel oxide phase. The precursor particulates of Examples 4-8 contain a rock-salt phase in addition to the cubic spinel phase, with the amount of rock-salt phase increasing as the Ni content increases. The precursor particulate of Example 8 has the rock-salt phase as its majority phase and a cubic spinel phase as a minority phase.

[0123] Table 1 The feedstock component Ni:Mn:Co molar ratio (x:y:z), the amount of each feedstock component used to make each precursor particulate, and the phases present in each precursor particulate of Example 1-8. Here CS = cubic spinel, TS = tetragonal spinel, RS = rock-salt. Feedstock Component Molar Amount of Each Feedstock Ratio Component Used (g) phases Example x (Ni) y (Mn) z (Co) NiO Mn3O4Co3O4present 1 0.048 0.476 0.476 0.4554 4.6505 4.8941 CS, TS, RS 2 0.070 0.465 0.465 0.6679 4.5469 4.7851 CS 3 0.091 0.455 0.455 0.8712 4.4479 4.6809 CS 4 0.111 0.444 0.444 0.5329 2.1765 2.2906 CS, RS 5 0.200 0.400 0.400 1.9262 3.9338 4.1400 CS, RS 6 0.273 0.364 0.364 2.6356 3.5882 3.7762 CS, RS 7 0.333 0.333 0.333 1.6151 1.6492 1.7356 CS, RS 8 0.600 0.200 0.200 5.8873 2.0039 2.1088 RS, CS

[0124] SEM images show that the precursor particulates of Examples 1-8 are in the form of powders with particle sizes in the range of 0.1 - 10 μm. Figure 6(a-c) shows EDS compositional maps of the precursor particulates of Examples 1-8. As shown in Figure 6(b), precursor particulates of Examples 2 and 3 show a homogeneous distribution of Mn amongst the precursor particles, within the resolution of the detector. However the precursor particulates of Examples 1 and 3-8 all show regions of high Ni (as shown in Figure 6(a)) and low Mn concentrations (as shown in Figure 6(b)) in their EDS compositional maps. The amount of compositional inhomogeneity in Ni, Co, and Mn in Examples 3-8 increased with increasing Ni content (as shown in Figure 6(a-c)). That is, theamount of compositional inhomogeneity in all samples increased with increasing amount of rock-salt phase in the sample.

[0125] Examples 9—16

[0126] The precursor particulates of Examples 1-8 were triturated by automatic mortar grinder with NiO powder as a second nickel source and Li2CO3 powder (99%, Alfa Aesar) as a lithium source. The amounts of each precursor component used in the making of Examples 9-16 was according to the amount required to produce a product LiNMC with a stoichiometry of LiNi0.6Mn0.2Co0.2O2, excepting that the lithium source used was in 5% excess. The precursor particulate used and the total amounts of each precursor component used in the making of Examples 9-16 is listed in Table 2. After triturating, the resulting precursor mixtures were heated in air at 5°C / min from 20°C to 650°C, then held isothermally at 650°C for 1 hour, then heated at 5°C / min from 650°C to 900°C, then held isothermally at 900°C for 12 hours, and then the furnace was allowed to naturally cool to 20°C. The resulting product LiNMC samples were then ground by mortar and pestle.

[0127] Table 2 The precursor particulate, and the amounts of each precursor component (precursor particulate, Li2CO3 as a lithium source, and NiO as a second nickel source) used in the precursor combining procedure in the making of Examples 9-16. Precursor Precursor Particulate Li2CO3NiO Particulate Amount Amount Amount Example Used (g) (g) (g) 9 Example 1 2.8609 3.3792 3.7663 10 Example 2 2.9294 3.3706 3.7000 11 Example 3 2.9983 3.3681 3.6336 12 Example 4 2.9338 3.6844 3.4136 13 Example 5 3.2668 3.6849 3.1035 14 Example 6 3.5838 3.6694 2.7815 15 Example 7 3.9108 3.6655 2.4700 16 Example 8 6.4263 3.5922

[0128] Table 3 The lattice constants, the standard deviation in the “c” lattice parameter, and the electrochemical characteristics of the product LiNMC of Examples 9- 16. Here ICE = initial coulombic efficiency, P is the voltage polarization at cycle 1, and Q(100) is the discharge capacity at cycle 100.a c σcICE P Q(100) Example (Å) (Å) (%) (%) (V) (mAh / g) 9 2.8718 14.2192 0.118 87.1 0.054 112.7 10 2.8729 14.2258 0.050 88 0.065 126.1 11 2.8710 14.2198 0.060 89.9 0.061 103.6 12 2.8729 14.2346 0.099 85.8 0.075 107.9 13 2.8745 14.2315 0.091 84.7 0.123 37.9 14 2.8797 14.2487 0.144 86.9 0.112 70.4 15 2.8740 14.2319 0.106 76.4 0.100 48.4 16 2.8708 14.2216 0.070 82.9 0.107 108.8

[0129] Figure 7 shows SEM images of the product LiNMC samples of Examples 9-16. The average particle sizes of these examples are all in the range between 2 μm and 10 μm.

[0130] Figure 8 shows XRD patterns of the product LiNMC of Examples 9-16. All samples are phase pure LiNMC with the O3 structure, indicating full conversion of the precursor mixtures to a layered oxide crystal structure. From these XRD patterns, lattice constants / lattice parameters were obtained and are listed in Table 3. The product LiNMC XRD peak widths and positions were used to calculate the standard deviation in the lattice parameter c (σc) according to the Williamson-Hall method. These values are listed in Table 3 and are related to the compositional inhomogeneity in the LiNMC, with larger values of σc indicating larger compositional inhomogeneity. The lowest values of σc were obtained the LiNMC of Examples 10 and 11, which are the samples in which the precursor particulate consisted essentially of a cubic spinel oxide phase. This indicates that that the product LiNMC of Examples 10 and 11 were the highest level of compositional homogeneity of all the examples.

[0131] The LiNMC of Examples 9-16 were incorporated into coin- configuration half-cells for electrochemical analysis. Figure 9 shows the voltage curves of the first cycle for each of the product LiNMC of Examples 9-16. From these voltage curves the initial coulombic efficiency (ICE) and voltage polarization were calculated. These values are listed in Table 3. The highest ICE was obtained for the LiNMC of Examples 10 and 11. These samples also had amongst the lowest polarization values of all the examples. This is desirable for good performance in practical devices. Figure 10 shows the capacity as a function of cycle number of the product LiNMC of Examples 9-16. Reversible charge / discharge cycling was observed for all these examples, however some examples exhibited better capacity retention than others. Table 3 lists the discharge specific capacityobtained at 100 cycles of Examples 9-16. The highest discharge specific capacity after 100 cycles was obtained for the LiNMC of Example 10, which is desirable for good performance in consumer or commercial devices.

[0132] Notable is that the product LiNMC of Example 10, which was made according to the present invention, has a greater compositional homogeneity, lower voltage polarization, higher initial coulombic efficiency, and higher specific capacity after 100 cycles (all desirable traits) than the product LiNMC of Example 16, which was made with a precursor particulate of the same composition as the LiNMC for NMC622 and no second source of nickel was added after a first heating.

[0133] Examples 17-19

[0134] The LiNMC of Examples 17-19 were made in the same way as Examples 9-11, excepting that a 20% excess of the Li2CO3lithium source was used and also a different precursor mixture heating procedure was used. The precursor particulate used and the actual amounts of each precursor component used in the making of Examples 17-19 are listed in Table3. The precursor mixture heating procedure was as follows: First the precursors mixtures were heated in the same way as the precursor mixtures were heated in Examples 9-16: heated in air at 5°C / min from 20°C to 650°C, then held isothermally at 650°C for 1 hour, then heated at 5°C / min from 650°C to 900°C, then held isothermally at 900°C for 12 hours, and then the furnace was allowed to naturally cool to 20°C. The precursor mixture samples were then heated and naturally cooled again under the same conditions, except under a flow of oxygen gas, instead of air. In these heating procedures the samples were not removed from the furnace (and no additional components were added) between the two heating steps– after the first heating procedure in air, the gas was switched to oxygen and the second heating procedure was then performed in the same furnace. The resulting product LiNMC samples were then ground by mortar and pestle.

[0135] Table 4 The precursor particulate, and the amounts of each precursor component (precursor particulate, Li2CO3as a lithium source, and NiO as a second nickel source) used in the precursor combining procedure in the making of Examples 17-19.Precursor Precursor Particulate Li2CO3NiO Particulate Amount Amount Amount Example Used (g) (g) (g) 17 Example 1 2.6450 3.5705 3.4821 18 Example 2 2.7954 3.6739 3.5307 19 Example 3 2.9983 3.8493 3.6336

[0136] Table 5 The lattice constants, the standard deviation in the “c” lattice parameter, and the electrochemical characteristics of the product LiNMC of Examples 17- 19. Here ICE = initial coulombic efficiency, P is the voltage polarization at cycle 1, and Q(100) is the discharge capacity at cycle 100. a c σcICE P Q(100) Example (Å) (Å) (%) (%) (V) (mAh / g) 17 2.8659 14.2081 0.053 89.0 0.038 127.3 18 2.8649 14.2053 0.064 90.3 0.043 159.5 19 2.8668 14.2103 0.076 86.7 0.028 145.3

[0137] Figure 11 shows SEM images of the product LiNMC samples of Examples 17-19. The LiNMC particulate of Example 18 has an average particle size in the range of 5—10 µm. The LiNMC particulates of Examples 17 and 19 have average particle sizes in the range of 10—15 µm.

[0138] Figure 12 shows the XRD patterns of the product LiNMC of Examples 17-19. All samples are phase pure LiNMC with the O3 structure, indicating full conversion of the precursor mixtures to a layered oxide crystal structure. From these XRD patterns values of the lattice constants were obtained and are listed in Table 5. The product LiNMC XRD peak widths and positions were used to calculate the standard deviation in the lattice parameter c (σc) according to the Williamson-Hall method. These values are listed in Table 5 and are related to the compositional inhomogeneity in the LiNMC, with larger values of σcindicating larger compositional inhomogeneity. The σcvalues of Examples 18 and 19 are comparable to those of Examples 10 and 11, which use the same respective precursor particulate. The σcvalue of Example 17 is significantly lower than that of Example 9, which uses the same precursor particulate. This indicates that the process used in Examples 17-19 improves on the homogeneity of the LiNMC of Example 9, to a level that is comparable to that of Examples 10 and 11, but does not improve the homogeneity of the LiNMC of Examples 10 and 11 further, within the detection limits of the Williamson-Hall method. This shows that a single-phase precursor (used in Examples 10 and 11) shows advantageousresults compared to a multi-phase precursor (used in Example 9), as a cubic spinel single- phase precursor does not require extra heating steps to improve homogeneity.

[0139] The LiNMC of Examples 17-19 were incorporated into coin- configuration half-cells for electrochemical analysis. Figure 13 shows the voltage curves of the first cycle for each of the product LiNMC of Examples 17-19. From these voltage curves the initial coulombic efficiency (ICE) and voltage polarization were calculated. Figure 14 shows the capacity as a function of cycle number of the product LiNMC of Examples 17-19. Table 5 lists the discharge specific capacity obtained at 100 cycles. The voltage polarization of cycle 1 is improved (lower) in all cases for Examples 17-19 compared to Examples 9-11. The specific capacity obtained after 100 cycles is also significantly improved (higher) for Examples 17-19 compared to Examples 9-11. The highest capacity after 100 cycles was obtained for Example 18. Examples 18 and 19 both have higher capacities after 100 cycles compared to Example 17, indicating the pure CS precursor produced an NMC with improved electrochemical results compared to when a multi-phase precursor was utilized. Additional Notes

[0140] 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.

[0141] 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 otherwise.

[0142] 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 wereexplicitly 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 + / - 5%) from the stated value.

[0143] 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.

[0144] 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. The accompanying claims and their equivalents are intended to cover such forms or modifications as would fall within the scope and spirit of the disclosure.

[0145] 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.

[0146] 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 somecases, be excised from the combination, and the combination may be claimed as a sub- combination or variation of a sub-combination.

[0147] 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 should not 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.

[0148] 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.

[0149] 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.

[0150] 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.

[0151] 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.

[0152] 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.

[0153] 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.

[0154] 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. 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.

[0155] 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 is intended 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 nickel manganese cobalt oxide cathode material having the formula Li1+p[(NinMnmCoc)1-aAa]1-pO2, where -0.03 ≤ p ≤ 0.06; n + m + c = 1; n ≥ 0.50; m ≥ 0.05; c ≥ 0; A is an optional metal dopant; and 0 ≤ a ≤ 0.05; the method comprising: obtaining feedstock components that include a nickel source, a manganese source, and a cobalt source; combining the feedstock components in a feedstock component Ni:Mn:Co:A molar ratio of x:y:z:w, where x + y + z = 1, x ≥ 0, 0.10 ≤ y ≤ 0.90, z ≥ 0, and 0 ≤ w ≤ 0.05 to produce a feedstock mixture; heating the feedstock mixture in an oxygen containing atmosphere to a temperature greater than about 450°C according to a feedstock mixture heating procedure to obtain a precursor particulate; combining precursor components that include the precursor particulate, a lithium source, and a second nickel source to obtain a precursor mixture, wherein the precursor components are combined such that the total amount of Ni, Mn, Co, and dopant A, are substantially equal to the stoichiometric amounts required to make the lithium nickel manganese cobalt oxide cathode material and in which the lithium is greater than or equal to the stoichiometric amounts required to make the lithium nickel manganese cobalt oxide cathode material; and heating the precursor mixture in an oxygen containing atmosphere at a temperature greater than about 700°C according to a precursor mixture heating procedure to obtain the lithium nickel manganese cobalt oxide cathode material.

2. The method according to claim 1 wherein c ≥ 0.

05.

3. The method according to claim 1 or 2 wherein z > 0.

4.

4. The method according to claim 1 wherein x + y + z = 1, 0 ≤ w ≤ 0.05, and wherein the Ni, Mn, and Co content of the precursor particulate composition is defined to be within a region of the Ni-Mn-Co ternary composition diagram bounded by the line segments ακ, κν, νδ, δε, εξ, and ξα where α = Mn0.2Co0.8, κ = Mn0.8Co0.2, ν = Ni0.2Mn0.8, δ = Ni0.47Mn0.53, ε = Ni0.47Mn0.36Co0.17, and ξ = Ni0.8Co0.2.

5. The method according to claim 1 wherein x + y + z = 1, 0 ≤ w ≤ 0.05, and where the Ni, Mn, and Co content of the precursor particulate composition is defined to be within a region of the Ni-Mn-Co ternary composition diagram bounded by the line segments αβ, βγ, γδ, δε, εζ, ζη, and ηα where α = Mn0.2Co0.8, β = Mn0.5Co0.5, γ = Ni0.25Mn0.75, δ = Ni0.47Mn0.53, ε = Ni0.47Mn0.36Co0.17, ζ = Ni0.30Mn0.36Co0.34, and η = Ni0.1Mn0.1Co0.

8.

6. The method according to claim 1 wherein x + y + z = 1, 0 ≤ w ≤ 0.05, and where the Ni, Mn, and Co content of the precursor particulate composition is defined to be within a region of the Ni-Mn-Co ternary composition diagram bounded by the line segments σβ, βγ, γτ, and τσ where σ = Mn0.3Co0.7, β = Mn0.5Co0.5, γ = Ni0.25Mn0.75, τ = Ni0.40Mn0.

60.

7. The method according to claims 4 to 6 wherein the precursor particulate consists essentially of a spinel phase.

8. The method according to claim 7 wherein the precursor spinel phase contains all of the Mn and Co required to synthesize the lithium nickel manganese cobalt oxide cathode material.

9. The method of claim 1, wherein the precursor components additionally comprise a second cobalt source.

10. The method of any one of claims 1-9, wherein the combining to obtain a precursor mixture is a dry mixing process.

11. The method of any one of claims 1-10, wherein the combining to obtain a feedstock mixture is a dry mixing process.

12. The method of any one of claims 1-11, additionally comprising adding a flux during the heating of the feedstock mixture or the precursor mixture.

13. An all-dry method of preparing a lithium nickel manganese cobalt oxide material, the method comprising: obtaining feedstock components that include a nickel source, a manganese source, and a cobalt source; dry mixing the feedstock components to obtain a feedstock mixture, wherein the molar amount of Ni is about 47% or less than the molar amounts of manganese and cobalt individually; heating the feedstock mixture an oxygen containing atmosphere from a temperature below about 50°C to an elevated temperature between about 700°C to about 1200°C and holding at the elevated temperature for at least an hour;cooling the feedstock mixture to a temperature below about 100°C to obtain a nickel manganese cobalt oxide precursor particulate having a majority phase of cubic spinel oxide.

14. The method of claim 13, additionally comprising dry mixing the nickel manganese cobalt oxide precursor particulate with a lithium source and a second nickel source to obtain a precursor mixture.

15. The method of claim 14, additionally comprising heating the precursor mixture in an oxygen containing atmosphere from a temperature below about 50°C to one or more elevated temperatures between about 700°C to about 1600°C and holding at the one or more elevated temperatures for at least an hour followed by cooling to below about 50°C to obtain a lithium nickel manganese cobalt oxide cathode material.

16. The method of claim 15, wherein the lithium nickel manganese cobalt oxide cathode material has the formula LiNi0.6Mn0.2Co0.2O2.

17. The method of claims 15 or 16, additionally comprising deagglomerating the lithium nickel manganese cobalt oxide cathode material.

18. The method of any one of claims 13-17, wherein the molar amount of Ni is about 20% or less than of the molar amounts of manganese and cobalt individually.

19. A nickel manganese cobalt oxide precursor particulate comprising: a cubic spinel oxide phase as the majority phase; wherein the nickel manganese cobalt oxide precursor particulate is within a region of the Ni-Mn-Co ternary composition diagram bounded by the line segments ακ, κν, νδ, δε, εξ, and ξα where α = Mn0.2Co0.8, κ = Mn0.8Co0.2, ν =and solvent residues; wherein the nickel manganese cobalt oxide precursor particulate consists essentially of nickel manganese cobalt oxide precursor materials homogeneously distributed on an atomic scale.

20. The nickel manganese cobalt oxide precursor particulate of claim 19, wherein the molar amount of Ni is about 20% or less than of the molar amounts of manganese and cobalt individually.

21. The nickel manganese cobalt oxide precursor particulate of claims 19 or 20, wherein the precursor particulate composition is defined to be within the region of the Ni- Mn-Co ternary composition diagram bounded by the line segments αβ, βγ, γδ, δε, εζ, ζη,and ηα where α = Mn0.2Co0.8, β = Mn0.5Co0.5, γ = Ni0.25Mn0.75, δ = Ni0.47Mn0.53, ε = Ni0.47Mn0.36Co0.17, ζ = Ni0.30Mn0.36Co0.34, and η = Ni0.1Mn0.1Co0.

8.

22. The nickel manganese cobalt oxide precursor particulate of claim 19, additionally comprising minority phases of rock-salt and tetragonal spinel.

23. The nickel manganese cobalt oxide precursor particulate of claim 19, wherein the nickel manganese cobalt oxide precursor particulate consists essentially of cubic spinel oxide phase.

24. A battery containing the lithium nickel manganese cobalt oxide material produced according to Claims 1 or 13.

Images