Methods for reducing gamma-NiOOH in battery materials

Abstract

Disclosed is a method for preparing a battery material, comprising heat-treating an aqueous suspension containing partially delithiated lithium nickel oxide (DLNO) to form a heat-treated suspension, and contacting the heat-treated suspension with an aqueous medium containing KOH at a temperature between 20°C and 90°C to form a stabilized slurry containing solids of the battery material. The ratio of the mass of KOH in the aqueous medium to the mass of DLNO in the heat-treated suspension can be from about 0.2 to about 0.03.

Description

[Technical Field]

[0001] The present disclosure relates to methods for improving the quality of intermediate products in battery material manufacturing. More specifically, the present disclosure relates in some embodiments to methods for treating partially delithiated lithium nickel oxide (DLNO) materials obtained from the delithiation of lithium nickel oxide (e.g., LiNiO) materials to reduce the formation of γ-NiOOH in acidic and / or caustic-treated stabilized battery materials. [Background technology]

[0002] Lithium-ion batteries are increasingly being used in essential applications such as electric vehicles, mobile phones, and cameras. The formation of battery materials for use in batteries typically involves two major steps. First, a precursor can be formed by a process such as coprecipitation, in which transition metals are mixed in the form of hydroxides or carbonates to form a precursor powder. This precursor can then be mixed with a lithium compound and calcined at elevated temperatures to form an electrochemically active composition. While forming battery materials according to conventional processes, the electrochemically active composition can be subjected to delithiation to remove the lithium while maintaining the crystalline arrangement of the other elements in the resulting delithiated electrochemically active composition. This allows the battery material prepared from the delithiated electrochemically active composition to be incorporated into a "charged" electrochemical cell as the cathode active material. Summary of the Invention [Problem to be solved by the invention]

[0003] Previous processes for achieving this delithiation of electrochemically active compositions have suffered from several drawbacks, such as undesirably high amounts of the γ-NiOOH phase in the battery material. The γ-NiOOH phase can undesirably form on the surface of the delithiated electrochemically active composition upon contact with alkaline solutions typically found in electrolytes used in battery fabrication. Because excess γ-NiOOH phase degrades battery quality, there is a need to develop techniques to reduce the formation of the γ-NiOOH phase on the delithiated electrochemically active composition. [Means for solving the problem]

[0004] The following summary is provided to facilitate an understanding of some of the innovative features unique to the present disclosure and is not intended to be a complete description. A complete understanding of the various aspects of the present disclosure can be obtained by taking the entire specification, claims, drawings, and abstract as a whole.

[0005] In one or more embodiments of the present disclosure, there is provided a method for preparing a battery material, the method comprising: x Ni z O2 (wherein x is in the range of about 0.2 to about 0.2 and z is in the range of about 0.1 to about 1) is mixed with an aqueous medium to form Li x Ni z Obtaining an aqueous suspension containing O2; Li x Ni z heat-treating an aqueous suspension containing O for a first heat-treatment time and a first heat-treatment temperature to form a heat-treated suspension; contacting the heat-treated suspension with an aqueous medium containing an alkali, alkaline earth hydroxide, KOH, or a combination thereof at a second temperature of about 20°C to about 90°C to form a stabilized slurry containing battery material solids and a filtrate, wherein the moles of hydroxide of alkali, alkaline earth hydroxide, KOH, or a combination thereof in the aqueous medium and the moles of Li in the heat-treated suspension are x Ni z the ratio of the number of moles of O2 to the number of moles of O2 is about 0.03 to about 0.2); and filtering the stabilized slurry to separate the solids from the filtrate. [Brief explanation of the drawings]

[0006] [Figure 1] FIG. 1 is a graph of the XRD analysis of various structures of nickel hydroxide. [Figure 2] FIG. 2 is a diagram of an exemplary process of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0007] It should be understood that the following disclosure describes several exemplary embodiments for implementing different features, structures, and / or functions of the present invention. While exemplary embodiments of components, arrangements, and configurations are described below to simplify the disclosure, these exemplary embodiments are provided merely as examples and are not intended to limit the scope of the present invention. Furthermore, the present disclosure may repeat reference numerals and / or letters in various exemplary embodiments and throughout the figures provided herein. This repetition is for the purposes of simplicity and clarity and does not, as such, dictate a relationship between the various exemplary embodiments and / or configurations discussed in the figures. Furthermore, an exemplary embodiment may be used in any other exemplary embodiment without departing from the scope of the present disclosure.

[0008] The present disclosure is directed to methods for treating delithiated electrochemically active compositions to reduce the formation of γ-NiOOH. These delithiated electrochemically active compositions may comprise intermediate materials suitable for use as battery materials in electrochemical cells, such as one or more cells in a primary or secondary battery. Cost-effective methods for treating delithiated electrochemically active compositions to reduce the production of γ-NiOOH are provided.

[0009] The gamma phase (γ-NiOOH) is one of four nickel hydroxide structures. In Ni(II), aging of α-Ni(OH)2 forms β-Ni(OH)2. In Ni(III), aging of β-NiOOH forms γ-NiOOH. When α-Ni(OH)2 forms β-Ni(OH), disorder at low 2θ can be observed. When measured by X-ray diffraction (XRD), γ-NiOOH can exhibit an XRD peak at approximately 12.5° 2θ, as shown in Figure 1. The relative amount of γ-NiOOH can be estimated by evaluating the XRD peak at approximately 12.5° 2θ relative to the peak height of other phases or internal standards.

[0010] The present disclosure provides a process for producing a battery material having a low amount of γ-NiOOH. In one or more examples, the production of the battery material can begin with the calcination of a lithium compound and a transition metal compound, a rare earth element compound, or a combination thereof. In some examples, the lithium compound can include lithium hydroxide and the transition metal compound can be Ni(OH), resulting in LNO (lithium nickel oxide) as a material precursor for the battery material.

[0011] As used herein, the term "lithium compound" refers to a lithium-containing composition in the form of lithium hydroxide, lithium oxide, lithium carbonate, lithium nitrate, lithium sulfate, lithium acetate, lithium peroxide, lithium bicarbonate, or lithium halide.

[0012] The transition metal compound or rare earth compound can be selected from a metal, oxide, hydroxide, hydride, carbonate, hydroxycarbonate, bicarbonate, nitrate, sulfate, acetate, halide, or one or more combinations thereof.

[0013] As used herein, the term "calcining" refers to a heat treatment in the presence of an oxidizing atmosphere that causes a chemical change in a material.

[0014] As used herein, the term "electrochemically active composition" refers to the active battery material precursors that have been subjected to calcination.

[0015] As used herein, the term "delithiated electrochemically active composition" refers to an electrochemically active composition that has been subjected to one or more delithiation processes. An example of a delithiated electrochemically active composition can include delithiated LiNiO, also referred to herein as "DLNO."

[0016] A "delithiation process" may include a process that reduces the atomic percent (at%) of lithium on a metal basis. In one or more examples, the delithiation process may be a Ca / Na / Li hypochlorite delithiation process. One or more exemplary delithiation techniques are disclosed in WO2021183094, which is incorporated herein by reference.

[0017] Illustrative examples of electrochemically active compositions include, but are not limited to, LiNiMO-based chemistries, where M is any element in the material and can be any transition metal, rare earth element, or combination thereof.

[0018] A process for removing lithium from an electrochemically active composition may include providing an electrochemically active composition, combining the electrochemically active composition with a strong oxidizing agent or an acid cleaner for a lithium removal time, and thereby forming a delithiated electrochemically active composition. Briefly, the delithiation process involves removing Li y Ni zThe method can include combining an electrochemically active composition defined by the formula MO2 (wherein M is optionally one or more metals, transition metals, rare earth metals, or combinations thereof) with a strong oxidizing agent for a delithiation time such that the at% ratio of Li / Ni after the delithiation time is less than the initial at% ratio of Li / Ni. The strong oxidizing agent can include one or more of hypochlorite, chlorite, chlorate, perchlorate, hydrogen peroxide, chlorine, hypochlorous acid, or ozone.

[0019] The delithiated electrochemically active composition after being subjected to the delithiation process or processes has the formula Li y Ni z The delithiated electrochemically active composition may include compositions corresponding to the formula MO2, where y is the atomic ratio of Li, typically between 0 and 0.2, and z is the atomic ratio of Ni, ranging from 0.1 to 1. M may be an additive and may be one or more of Co, Mn, Al, Mg, Ti, Zr, Nb, Hf, V, Cr, Sn, Cu, Mo, W, Fe, Si, Zn, B, other transition metals, rare earth elements, or combinations thereof. In some embodiments, M is 1, 2, 3, 4, 5, or more from the foregoing list. In one or more embodiments, the ratio of Ni to M may be from about 1:1 to about 100:about 1, about 200:about 1, about 300:about 1, up to about 500:about 1, or more. In one or more examples, the delithiated electrochemically active composition may be free of M.

[0020] The atomic ratio of Li can be measured by any process known in the art. Examples include inductively coupled plasma atomic emission spectroscopy (ICP) or atomic absorption spectroscopy as described by JR Dean (Practical Inductively Coupled Plasma Spectroscopy, Chichester, England: Wiley, 2005, 65-87) and Welz and Sperling (Atomic Absorption Spectroscopy, 3rd Edition, Weinheim, Germany: Wiley VCH, 1999, 221-294). The chemical composition of the composition can be determined using a Varian Liberty 100 inductively coupled plasma (ICP) system.

[0021] The delithiated electrochemically active composition can include Ni and one or more additives. In one or more examples, the delithiated electrochemically active composition includes an atomic percentage (at%) of Ni, based on the total of additives M in the electrochemically active composition, of 10 at% or more, optionally 20 at% or more, optionally 30 at% or more, optionally 40 at% or more, optionally 50 at% or more, optionally 60 at% or more, optionally 70 at% or more, optionally 80 at% or more, optionally 90 at% or more, optionally 95 at% or more, optionally 96 at% or more, optionally 97 at% or more, optionally 98 at% or more, optionally 99 at% or more, or optionally 100 at%. Optionally, the atomic percentage of Ni can be from 70 at% to 99 at% or more. Optionally, the atomic percentage of Ni can be from 80 at% to 99 at% or more. Optionally, the atomic percentage of Ni can be from 90 at% to 99 at% or more. Optionally, Ni can be the only transition metal designed into or present in the material, such that Ni can be present at substantially 100 at%. In one or more embodiments, the ratio of Ni to M can be from about 1:1 to about 100:1, about 200:1, about 300:1, up to about 500:1 or more.

[0022] Optionally, the delithiated electrochemically active composition can include Ni and one or more other transition metals. If included, the one or more other transition metals (other than Ni) can each be individually present at 0 at% to 5 at%. Optionally, the one or more other transition metals can each be individually present at 0.1 at% to 4.5 at%, optionally 0.5 at% to 4 at%. Optionally, one, two, three, or more other transition metals other than Ni can be present in the delithiated electrochemically active composition.

[0023] Delithiated electrochemically active compositions, such as DLNO, have a particle size. Particle size is defined as Dv50, which is the diameter of particles such that approximately 50% of the sample's mass is smaller than Dv50 and approximately 50% of the sample's mass is greater than Dv50, assuming particle density is uniform and not a function of size. Optionally, the particle size can be 1-20 μm or any value or range therebetween. Optionally, the particle size can be about 1 μm to about 15 μm, optionally about 1-10 μm, optionally about 1-7 μm, optionally about 4-7 μm, or optionally about 4-6 μm. Particle size can be measured by techniques known in the art, such as laser diffraction particle size analysis. Laser diffraction particle size analysis can measure particle size distributions by measuring the angular change in the intensity of light scattered as a laser beam passes through a dispersed particulate sample. Larger particles scatter light at smaller angles relative to the laser beam, while smaller particles scatter light at relatively larger angles. The angular scattering intensity data can be analyzed and the Mie theory of light scattering can be used to calculate the size of the particles responsible for producing the scattering pattern. Particle size can be reported as volume-equivalent spherical diameter.

[0024] Often, electrochemically active compositions that have been subjected to a delithiation process, such as DLNO, are too chemically reactive to be used directly as battery materials in battery cells. Therefore, the delithiated electrochemically active compositions can be subjected to a stabilization treatment.

[0025] Referring to LNO as an exemplary material precursor for such stabilization, LNO can be treated with an aqueous oxidation process that partially oxidizes Ni(III) to Ni(IV), effectively substantially delithiating LNO, thereby forming DLNO (delithiated nickel oxide) as a first intermediate product. To stabilize the intermediate product for direct use in a battery cell, the intermediate product can be partially stabilized (reduced) by exposure to an alkali, alkaline earth hydroxide, KOH, or a combination thereof, thereby forming stabilized delithiated nickel oxide (e.g., "KDLNO"). This KDLNO is sufficiently stable to be suitable not only as a battery material but also for other applications.

[0026] The order and approximate chemical formula of the materials at various stages is shown below: LNO-LiNi z O2 (the oxidation state of nickel is approximately 2.9 to 3.0) DLNO-Li x Ni z O2 (the oxidation state of nickel is approximately 3.7 to 4.0) KDLNO-K y Li x Ni z O2 (the oxidation state of nickel is approximately 3.5 to 4.0) (wherein y ranges from about 0 to 0.3, x ranges from about 0 to 0.2, z ranges from about 0.1 to 1, and x+y can range from about 0 to 0.5).

[0027] It may be advantageous to prepare the battery material in a manner that reduces the formation of γ-NiOOH in the battery material, such as by pretreating the delithiated nickel oxide before converting it to potassium-stabilized delithiated nickel oxide.

[0028] As shown in FIG. 2, the method for preparing the battery material includes: a) Li x Ni z O2 is mixed with an aqueous medium to x Ni zb) obtaining an aqueous suspension containing Li x Ni z The method may include the steps of: heat-treating an aqueous suspension containing O for a first heat-treatment time and a first heat-treatment temperature to produce a heat-treated suspension; c) contacting the heat-treated suspension with an aqueous medium containing alkali, alkaline earth hydroxide, KOH, and / or combinations thereof at a second temperature of 20°C to 90°C to produce a stabilized slurry containing battery material solids and a filtrate; and d) filtering the stabilized slurry to separate the solids from the filtrate.

[0029] In step a), Li x Ni z O2 can be a delithiated nickel oxide, where x ranges from 0 to 0.2 and z ranges from 0.1 to 1. In one or more examples, x can be 0.2 or less, 0.15 or less, 0.1 or less, or 0.05 or less. In one or more examples, z can be 0.1 or more, 0.15 or more, 0.2 or more, 0.25 or more, or 0.3 or more. In one or more examples, z can be 1 or less, 0.9 or less, 0.8 or less, 0.7 or less, or 0.5 or less.

[0030] Li x Ni z O2 is mixed with an aqueous medium to x Ni zIn step a) of obtaining an aqueous suspension containing O2, the aqueous medium can include water, deionized water, a dilute solution of alkali, alkaline earth hydroxide, KOH, or a combination thereof, or a regenerated filtrate. In one or more examples, in step a), the aqueous medium can include an alkali, alkaline earth hydroxide, KOH, or a combination thereof at a concentration of 1% or less based on the total mass of the aqueous medium. In one or more examples, the aqueous medium can include an alkali, alkaline earth hydroxide, KOH, or a combination thereof at a concentration of 0.75% or less, 0.50% or less, 0.45% or less, 0.40% or less, 0.35% or less, 0.30% or less, 0.25% or less, or 0.20% or less. In one or more examples, the aqueous medium can be obtained from the regenerated filtrate obtained in step d). The alkali or alkaline earth hydroxide can be selected from NaOH, LiOH, KOH, Ca(OH)2, or Mg(OH)2, or a combination thereof.

[0031] In one or more instances, Li x Ni z In step b) of heat-treating the aqueous suspension containing O2, the first heat treatment temperature can be in the range of about 50°C to about 90°C. For example, the first heat treatment temperature can be 50°C or higher, 55°C or higher, 60°C or higher, 70°C or higher, 65°C or higher, or 80°C or higher. Furthermore, the first heat treatment temperature can be 90°C or lower, 85°C or lower, 80°C or lower, 75°C or lower, 70°C or lower, 65°C or lower, or 60°C or lower.

[0032] Li x Ni z In step b) of heat-treating the aqueous suspension containing O2, the first heat treatment time can be about 2 hours or less. For example, the first heat treatment time can be 30 minutes or more, 35 minutes or more, 40 minutes or more, 45 minutes or more, 50 minutes or more, 60 minutes or more, or 90 minutes or more. Furthermore, the first heat treatment time can be 120 minutes or less, 115 minutes or less, 110 minutes or less, 100 minutes or less, 90 minutes or less, or 60 minutes or less.

[0033] Li x Ni zIn the step b) of heat-treating the aqueous suspension containing O2, the aqueous suspension contains 10 mass % to 60 mass % of Li x Ni z For example, the aqueous suspension may contain 10% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight or more, 30% by weight or more, or 35% by weight or more of Li. x Ni z Further, the aqueous suspension may contain less than 60 wt.%, less than 55 wt.%, less than 50 wt.%, less than 45 wt.%, less than 40 wt.%, or less than 35 wt.% Li. x Ni z May contain O2.

[0034] Li x Ni z After step b), heat-treating the aqueous suspension containing O2, the temperature of the heat-treated suspension can be altered before contacting the heat-treated suspension with the aqueous medium. In one or more examples, the temperature of the heat-treated suspension can be reduced before contacting the heat-treated suspension with the aqueous medium, e.g., the temperature can be reduced by at least 5°C, at least 10°C, at least 15°C, at least 20°C, at least 25°C, at least 30°C, or at least 40°C.

[0035] In step c), the heat-treated suspension is contacted with an aqueous medium containing an alkali, an alkaline earth hydroxide, KOH, or a combination thereof to obtain a stabilized slurry containing the battery material solid and a filtrate. x Ni z O2 is contacted with an alkali, alkaline earth hydroxide, KOH, or a combination thereof to form Li x Ni z O2 to K y Li x Ni z The resulting K can be stabilized by converting it to O2. y Li x Ni z O2 is obtained as the solid portion of the battery material in a stabilized slurry, and is also referred to herein as "KDLNO."

[0036] In step c) of contacting the heat-treated suspension with an aqueous medium, Li in the heat-treated suspension is x Ni z The ratio of moles of hydroxide of alkali, alkaline earth hydroxide, KOH or a combination thereof in the aqueous medium to moles of O2 is about 0.03 to about 0.2. For example, Li in the heat-treated suspension x Ni z The ratio of moles of hydroxide of alkali, alkaline earth hydroxide, KOH, or a combination thereof in the aqueous medium to moles of O2 can be less than 0.1, less than 0.09, less than 0.08, less than 0.07, less than 0.06, or less than 0.05. Additionally, the ratio of moles of Li in the heat-treated suspension can be less than 0.1, less than 0.09, less than 0.08, less than 0.07, less than 0.06, or less than 0.05. x Ni z The ratio of moles of hydroxide of alkali, alkaline earth hydroxide, KOH, or combinations thereof in the aqueous medium to moles of O2 is greater than 0.03, greater than 0.035, greater than 0.04, greater than 0.045, greater than 0.05, greater than 0.06, greater than 0.07, greater than 0.08, greater than 0.09, greater than 0.10, greater than 0.11, or greater than 0.12. In one or more embodiments, the Li in the heat-treated suspension x Ni z The ratio of moles of hydroxide of alkali, alkaline earth hydroxide, KOH, or a combination thereof in the aqueous medium to moles of O2 is between about 0.06 and about 0.12.

[0037] At the start of step c) of contacting the heat-treated suspension with an aqueous medium, Li x Ni z The O2 material can be present in an amount of 10% to 95% by weight based on the total weight of the heat-treated suspension and aqueous medium. x Ni z The O2 material can be present in an amount of at least 10 wt.%, at least 15 wt.%, at least 20 wt.%, at least 25 wt.%, at least 30 wt.%, or at least 35 wt.%, based on the total weight of the heat-treated suspension and the aqueous medium. x Ni zThe O2 material can be present in an amount of 95% by weight or less, 90% by weight or less, 85% by weight or less, 80% by weight or less, 75% by weight or less, 70% by weight or less, 65% by weight or less, 60% by weight or less, 55% by weight or less, or 50% by weight or less, based on the total weight of the heat-treated suspension and aqueous medium.

[0038] The aqueous medium can include an alkali, alkaline earth hydroxide, KOH, or a combination thereof, at a concentration ranging from about 1% by weight or less, based on the total weight of the aqueous suspension. For example, the aqueous medium can include an alkali, alkaline earth hydroxide, KOH, or a combination thereof, at a concentration ranging from about 1%, 0.9%, 0.75%, 0.05%, or 0.25% by weight or less, based on the total weight of the aqueous suspension.

[0039] Step c) of contacting the heat-treated suspension with an aqueous medium can be carried out at a second temperature between 20° C. and 90° C. For example, the second temperature is 20° C. or higher, 25° C. or higher, 30° C. or higher, 35° C. or higher, 40° C. or higher, 50° C. or higher, or 60° C. Furthermore, the second temperature can be 90° C. or lower, 85° C. or lower, 80° C. or lower, 75° C. or lower, or 60° C. or lower.

[0040] In step c), contacting the heat-treated suspension with an aqueous medium can be performed for a contact time of about 5 hours or less. For example, the first heat treatment time can be 5 minutes or more, 10 minutes or more, 15 minutes or more, 30 minutes or more, 45 minutes or more, 60 minutes or more, or 90 minutes or more. Furthermore, the first heat treatment time can be 300 minutes or less, 270 minutes or less, 240 minutes or less, 210 minutes or less, 180 minutes or less, or 140 minutes or less.

[0041] After step c) of contacting the heat-treated suspension with an aqueous medium to obtain a stabilized slurry containing the solids of the battery material and a filtrate, the method may include step d) of filtering the stabilized slurry to separate the solids from the filtrate.

[0042] Step d) can include filtering the stabilized slurry by a pressure or vacuum filtration process. In one or more examples, step d) of filtering the stabilized slurry to separate the solids from the filtrate can include filtering the stabilized slurry using a membrane filter press having a gauge feed pressure ranging from about -0.5 bar to about 7 bar, -0.25 bar to about 5 bar, 0 bar to about 3 bar, 0.5 bar to about 4 bar, 1 bar to about 3 bar, or any gauge pressure therebetween.

[0043] The filtrate from step d) can contain 0 to 5% by weight of KOH. The filtrate from step d) can contain less than 5% by weight of KOH, less than 4.5% by weight of KOH, less than 4% by weight of KOH, less than 3% by weight of KOH, less than 2% by weight of KOH, or less than 1% by weight of KOH.

[0044] Optionally, the filtrate can be recycled for use as a component of the aqueous medium or aqueous suspension.

[0045] The solid obtained from step d) of filtering the stabilized slurry to separate the solid from the filtrate can be obtained as a filter cake. The filter cake can be used as a battery material without washing. Alternatively, the filter cake can be washed with water, weak acid water, or weak caustic water.

[0046] Optionally, the method of the present disclosure may further comprise heat treating the solids separated from the filtrate in step d) for a second heat treatment time and a second heat treatment temperature.

[0047] The second heat treatment time can range from 30 minutes to 24 hours. For example, the second heat treatment time can be 30 minutes or more, 1 hour or more, 90 minutes or more, 2 hours or more, 3 hours or more, or 4 hours or more. Furthermore, the second heat treatment time can be 24 hours or less, 18 hours or less, 12 hours or less, or 6 hours or less.

[0048] The second heat treatment temperature can be in the range of 50° C. to 100° C. For example, the second heat treatment temperature can be 50° C. or higher, 55° C. or higher, 60° C. or higher, 65° C. or higher, 70° C. or higher, or 75° C. or higher. Furthermore, the temperature can be 100° C. or lower, 95° C. or lower, 90° C. or lower, 85° C. or lower, 80° C. or lower, 75° C. or lower, or 70° C. or lower.

[0049] In one or more examples, the method for preparing the battery material includes: a) dissolving Li x Ni z O2 is mixed with an aqueous medium to x Ni z a) obtaining an aqueous suspension containing O2; b) contacting the aqueous suspension with an aqueous medium containing KOH at a second temperature between 20°C and 90°C to produce a stabilized slurry containing the battery material solids and a filtrate; and d) filtering the stabilized slurry to separate the solids from the filtrate. The mixing, contacting, and filtering steps can be performed as described above.

[0050] Advantageously, the amount of γ-NiOOH in the solid obtained from the method of the present disclosure can be reduced, thereby improving the quality of KDLNO used as a battery material. The amount of γ-NiOOH in the solid can be measured by X-ray diffraction (XRD). In particular, the relative improvement in the amount of γ-NiOOH in the stabilized product is estimated by determining the ratio of the X-ray diffraction (XRD) peak intensity at about 12.5° 2θ to the XRD peak intensity at about 37.3° 2θ.

[0051] In X-ray diffraction analysis, an X-ray beam rotates on one axis to diffract a statistical distribution of crystallites, while simultaneously collecting data using a single-axis goniometer. Cu-Kα powder X-ray diffraction analysis is suitable for measuring X-ray diffraction peak intensities. In this application, a KDLNO sample is subjected to X-ray diffraction (XRD) using a Bruker D8 Advance XRD instrument to measure peak intensities at approximately 12.5°, 18.5°, and 37.3° 2θ. Using JADE v.8.2 software, an automatic background height determination without baseline smoothing is generated, and the maximum peak heights at 12.5°, 18.5°, and 37.3° are determined.

[0052] The stabilized battery material may have a ratio of the maximum intensity count (peak) of the solid state at about 12.5 degrees to the maximum intensity count (peak) at about 37 degrees as measured by Cu-Kα powder X-ray diffraction analysis of less than 1.0. For example, the ratio of the maximum intensity count (peak) of the solid state at about 12.5 degrees to the maximum intensity count (peak) at about 37 degrees as measured by Cu-Kα powder X-ray diffraction analysis may be less than 0.9, less than 0.8, less than 0.7, less than 0.6, less than 0.5, less than 0.4, less than 0.35, less than 0.3, less than 0.25, less than 0.2, or less than 0.1.

[0053] The stabilized battery material has a third X-ray diffraction peak intensity at a 2θ of about 18.5°, and the ratio of the third peak intensity to the second peak intensity at a 2θ of about 37.3° can be in the range of 10:100 to 40:100, 5:100 to 35:100, 10:100 to 30:100, 15:100 to 30:100, or 20:100 to 25:100.

[0054] The battery material obtained as a solid in step d) has the formula K y Li x Ni zM02, where x ranges from 0 to 0.2, y ranges from 0 to 0.3, z ranges from 0.1 to 1, x + y ranges from about 0 to 0.5, and M is optional and can be one or more of Co, Mn, Al, Mg, Ti, Zr, Nb, Hf, V, Cr, Sn, Cu, Mo, W, Fe, Si, Zn, B, other transition metals, rare earth elements, or combinations thereof. In one or more embodiments, the ratio of Ni to M can be from about 1:1 to about 100:about 1, about 200:about 1, about 300:about 1, up to about 500:about 1, or more.

[0055] In one or more examples, x can be 0 or greater, 0.05 or greater, 0.1 or greater, or 0.15 or greater. In one or more examples, x can be 0.2 or less, 0.15 or less, 0.1 or less, or 0.05 or less. In one or more examples, y can be 0.05 or greater, 0.1 or greater, or 0.15 or greater. In one or more examples, y can be 0.3 or less, 0.2 or less, 0.15 or less, or 0.1 or less. In one or more examples, z can be 0.1 or greater, 0.2 or greater, 0.3 or greater, 0.4 or greater, or 0.5 or greater. In one or more examples, z can be 1 or less, 0.9 or less, 0.8 or less, or 0.7 or less.

[0056] In one or more examples, the battery material can include 0.5% or more by weight of lithium, based on the total weight of the battery material. In one or more examples, the battery material can include 0.5% or more, 0.6% or more, 0.75% or more, 0.8% or more, or 0.9% or more by weight of lithium, based on the total weight of the battery material. In one or more examples, the battery material can include 1.1% or less by weight of lithium, based on the total weight of the battery material. In one or more examples, the battery material can include 1.05% or less, 1.0% or less, 0.95% or less, or 0.9% or less by weight of lithium, based on the total weight of the battery material.

[0057] In one or more examples, the battery material can include 50% or more by weight of nickel, based on the total weight of the battery material. In one or more examples, the battery material can include 55% or more, 60% or more, or 65% or more by weight of nickel, based on the total weight of the battery material. In one or more examples, the battery material can include 70% or less by weight of nickel, based on the total weight of the battery material. In one or more examples, the battery material can include 65% or less, 60% or less, or 55% or less by weight of nickel, based on the total weight of the battery material.

[0058] In one or more examples, the battery material can include 2% or more by weight of potassium, based on the total weight of the battery material. In one or more examples, the battery material can include 2.5% or more by weight, 3% or more by weight, or 4% or more by weight of potassium, based on the total weight of the battery material. In one or more examples, the battery material can include 6% or less by weight of potassium, based on the total weight of the battery material. In one or more examples, the battery material can include 5.5% or less by weight, 5% or less by weight, or 4% or less by weight of potassium, based on the total weight of the battery material.

[0059] The energy density of the battery material can be about 300 mAh / g to about 400 mAh / g. For example, the energy density of the battery material can be 310 mAh / g or more, 315 mAh / g or more, 320 mAh / g or more, 325 mAh / g or more, 330 mAh / g or more, 335 mAh / g or more, 340 mAh / g or more, or 350 mAh / g or more, or any combination thereof. For example, the energy density of the battery material can be 400 mAh / g or less, 395 mAh / g or more, 390 mAh / g or less, 385 mAh / g or less, 380 mAh / g or less, 375 mAh / g or less, 370 mAh / g or less, or 365 mAh / g or less.

[0060] The energy density of a battery material can be measured by incorporating the battery material into a battery and measuring the energy density of the resulting battery. The battery can have an anode including zinc (e.g., finely divided zinc), a zinc alloy, and / or zinc alloy particles. The battery can further include an alkaline electrolyte solution and a separator. The cathode can further include the battery material of the present disclosure. The cathode can further include 2% to 35% by weight (e.g., 5% to 20% by weight, 3% to 8% by weight, 10% to 15% by weight) of a conductive additive. Examples of conductive additives include graphite, carbon black, acetylene black, partially graphitized carbon black, silver powder, gold powder, nickel powder, carbon fiber, carbon nanofiber, carbon nanotube, and graphene. The electrolyte can include lithium hydroxide, sodium hydroxide, and / or potassium hydroxide. The separator can prevent soluble oxide species from diffusing from the cathode to the anode or capture soluble oxide species.

[0061] The battery material has a tap density of 1.8 g / cm after drying. 3 ~2.5g / cm 3 In one or more examples, the battery material may have a dry tap density in the range of 1.8 g / cm 3 More than 1.9g / cm 3 More than 2.0g / cm 3 More than 2.05g / cm 3 More than 2.1g / cm 3 or more, or 2.15 g / cm 3 The dry tap density of the battery material can be 2.5 g / cm or more. 3 Below, 2.4g / cm 3 Below, 2.3g / cm 3 Below 2.25g / cm 3 or less than 2.2g / cm 3A suitable technique for measuring dry tap density involves: 1) weighing a 250 mL graduate cylinder: M1; 2) filling the graduate cylinder with a KDLNO sample below the 250 mL line; 3) weighing the graduate cylinder + KDLNO powder: M2, where the mass of the KDLNO powder is M3 = M2 - M1; 4) measuring the volume of KDLNO in the graduate cylinder after 2500 taps with a Quantachrome autotap analyzer: V1. Dry tap density is calculated by dividing M3 by V1.

[0062] The present disclosure further relates to any one or more of the following numbered embodiments:

[0063] 1. A method for preparing a battery material, comprising: x Ni z O2 (wherein x is in the range of about 0 to about 0.2 and z is in the range of about 0.1 to about 1) is mixed with an aqueous medium to form Li x Ni z Obtaining an aqueous suspension containing O2; Li x Ni z heat-treating the aqueous suspension containing O for a first heat-treatment time and a first heat-treatment temperature to form a heat-treated suspension; contacting the heat-treated suspension with an aqueous medium containing an alkali, alkaline earth hydroxide, KOH, or a combination thereof at a second temperature of 20°C to 90°C to form a stabilized slurry containing battery material solids and a filtrate, wherein the moles of hydroxide of alkali, alkaline earth hydroxide, KOH, or a combination thereof in the aqueous medium and the moles of Li in the heat-treated suspension are x Ni z the ratio of the number of moles of O2 to the number of moles of O2 is about 0.03 to about 0.2; and filtering the stabilized slurry to separate the solids from the filtrate.

[0064] 2. The aqueous suspension is Li derived from a hypochlorite delithiation process. x Ni z Item 1. The method of claim 1, comprising O2.

[0065] 3. The method according to item 1 or 2, wherein the first heat treatment time is about 30 minutes to about 120 minutes; and the first heat treatment temperature is about 50°C to about 90°C.

[0066] 4. The method according to any one of items 1 to 3, wherein the first heat treatment time is about 40 to about 80 minutes and the first heat treatment temperature is about 65 to about 85°C.

[0067] 5. The method according to any one of items 1 to 4, wherein the heat-treated suspension is contacted with an aqueous medium containing an alkali, an alkaline earth hydroxide, KOH, or a combination thereof at a second temperature for a period of about 5 minutes to about 5 hours.

[0068] 6. The method according to any one of items 1 to 5, wherein the temperature of the heat-treated suspension is changed before contacting the heat-treated suspension with the aqueous medium.

[0069] 7. Li in the heat-treated suspension x Ni z 7. The method according to any one of items 1 to 6, wherein the molar ratio of the hydroxide of alkali, alkaline earth hydroxide, KOH, or a combination thereof in the aqueous medium to the molar ratio of O2 is about 0.06 to about 0.12.

[0070] 8. The method according to any one of items 1 to 7, wherein the filtrate contains about 0% to about 5% by mass of KOH.

[0071] 9. The method of any one of paragraphs 1 to 8, wherein one or more of the aqueous medium and the aqueous suspension comprises regenerated filtrate.

[0072] 10. The aqueous suspension contains about 10% by mass to about 60% by mass of Li x Ni z 10. The method of any one of paragraphs 1 to 9, comprising O2.

[0073] 11. The method according to any one of paragraphs 1 to 10, wherein the ratio of the maximum intensity count number of the solid at about 12.5 degrees to the maximum intensity count number at about 37 degrees, as measured by Cu-Kα powder X-ray diffraction analysis, is less than about 1.0.

[0074] 12. The method of any one of paragraphs 1 to 11, wherein filtering the stabilized slurry comprises a pressure or vacuum filtration process.

[0075] 13. The method according to any one of paragraphs 1 to 12, wherein the filter cake can be used unwashed or washed with water, weakly acidic water, or weakly caustic water.

[0076] 14. The method of any one of paragraphs 1 to 13, wherein the aqueous medium comprises an alkali, an alkaline earth hydroxide, KOH, or a combination thereof, at a concentration in the range of about 1% by weight or less, based on the total weight of the aqueous suspension.

[0077] 15. At the beginning of the contacting step, Li x Ni z Item 15. The method of any one of items 1 to 14, wherein the O2 material is present in an amount of 10% to 75% by weight based on the total weight of the suspension heat-treated in the aqueous medium.

[0078] 16. The method of any one of paragraphs 1 to 15, further comprising heat treating the solid separated from the filtrate for a second heat treatment time and at a second heat treatment temperature.

[0079] 17. The method according to any one of items 1 to 16, wherein the second heat treatment time is in the range of about 30 minutes to about 24 hours.

[0080] 18. The method according to any one of items 1 to 17, wherein the second heat treatment temperature is in the range of about 50°C to about 100°C.

[0081] 19. The method according to any one of items 1 to 18, wherein the battery material has an energy density in the range of about 300 mAh / g to about 400 mAh / g.

[0082] 20. The method according to any one of items 1 to 19, wherein the battery material comprises about 0.5% by mass to about 1.1% by mass of lithium, based on the total mass of the battery material, about 50% by mass to about 70% by mass of nickel, based on the total mass of the battery material, and about 2% by mass to about 6% by mass of potassium, based on the total mass of the battery material.

[0083] 21. The solid after drying has a density of about 1.8 g / cm 3 ~Approx. 2.5g / cm 3 21. The method according to any one of items 1 to 20, having a tap density in the range of

[0084] 22. Li x Ni z 22. The method of any one of paragraphs 1 to 21, wherein the O2 further comprises a concentration of one or more of Co, Mn, Al, Mg, Ti, Zr, Nb, Hf, V, Cr, Sn, Cu, Mo, W, Fe, Si, Zn, B, other transition metals, rare earth elements, or combinations thereof, totaling less than about 5% by weight.

[0085] 23. A method for preparing a battery material, comprising: x Ni z O2 (wherein x is in the range of about 0 to about 0.2 and z is in the range of about 0.1 to about 1) is mixed with an aqueous medium to form Li x Ni z obtaining an aqueous suspension containing O; contacting the aqueous suspension with a material containing an alkali, alkaline earth hydroxide, KOH, or a combination thereof at a second temperature of 20°C to 90°C to produce a stabilized slurry containing battery material solids and a filtrate, wherein the number of moles of hydroxide of alkali, alkaline earth hydroxide, KOH, or a combination thereof in the aqueous medium and the number of moles of Li in the heat-treated suspension are x Ni z the ratio of the number of moles of O2 to the number of moles of HCl is about 0.03 to about 0.2; and filtering the stabilized slurry to separate solids from the filtrate.

[0086] 24. Aqueous suspensions of Li derived from hypochlorite desorption processes x Ni z 24. The method of claim 23, comprising O2.

[0087] The foregoing description of the specific embodiment(s) is merely exemplary in nature and is in no way intended to limit the scope of the invention, its application, or uses, which may, of course, vary. The present disclosure is provided in conjunction with the non-limiting definitions and terms contained herein. These definitions and terms are not designed to serve as limitations on the scope or practice of the invention, but are presented for exemplary and descriptive purposes only. While a method or composition is described as a sequence of individual steps or using specific materials, it is understood that the steps or materials may be interchangeable, such that the description of the invention may include multiple parts or steps arranged in numerous ways, as readily understood by one of ordinary skill in the art.

[0088] Although terms such as "first," "second," and "third" may be used herein to describe various elements, components, regions, and / or steps, it will be understood that these elements, components, regions, layers, and / or steps are not limited by these terms. These terms are used only to distinguish one element, component, region, layer, or section from another element, component, region, layer, or section. Thus, a "first element," "component," "region," "layer," or "section" described above could be referred to as a second (or other) element, component, region, layer, or section without departing from the teachings herein.

[0089] The terms used herein are for the purpose of describing particular embodiments only and are not intended to be limiting. As used herein, the singular forms "a," "an," and "the" are intended to include the plural, including "at least one," unless the content clearly dictates otherwise. "Or" means "and / or." As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items. It will be further understood that the terms "comprise" and / or "comprising," or "including" and / or "comprising," as used herein, specify the presence of stated features, regions, integers, steps, operations, elements, and / or components, but do not exclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and / or groups thereof. The term "or combinations thereof" means combinations including at least one of the aforementioned elements.

[0090] Certain embodiments and features have been described using a set of upper numerical limits and a set of lower numerical limits. It should be understood that ranges including combinations of any two values, for example, any lower limit with any upper limit, any two lower limits, and / or any two upper limits, are contemplated unless otherwise indicated. Specific lower limits, upper limits, and ranges are set forth in one or more claims below. All numerical values ​​are "about" or "approximately" the indicated value, taking into account experimental error and variations that would be expected by one of ordinary skill in the art. Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.

[0091] Various modifications of the invention in addition to those shown and described herein will become apparent to those skilled in the art from the foregoing description, and such modifications are also intended to fall within the scope of the appended claims.

[0092] The patents, publications, and applications mentioned in this specification are indicative of the levels of those skilled in the art to which this invention pertains, and are herein incorporated by reference to the same extent as if each individual patent, publication, or application was specifically and individually indicated to be incorporated by reference.

[0093] The foregoing description illustrates certain embodiments of the present invention but is not intended to limit its practice.

[0094] Various aspects of the present invention will be illustrated by the following non-limiting examples, which are intended for illustrative purposes and are not intended to limit the scope of the present invention, and it will be understood that variations and modifications can be made without departing from the spirit and scope of the invention. [Example]

[0095] In the following examples, the first intermediate product of the battery material obtained from the delithiation process can be treated by the method of the present disclosure to reduce the amount of γ-NiOOH.

[0096] Example 1: Lithium nickel oxide (LNO) has a ClO of 0.87 - The DLNO was delithiated by treatment with LiClO at a molar ratio of 0.1% to 0.1%. The resulting DLNO was subjected to washing with DI-HO at 20 °C. The DLNO was subjected to heat treatment at 70 °C and stabilized by treatment with KOH to obtain the KDLNO sample. The sample was dried overnight at 70 °C before testing for 16–18 h.

[0097] The resulting KDLNO was subjected to X-ray diffraction (XRD) using a Rigaku Smartlab6 Advance XRD instrument to measure peak intensities at 2θ of approximately 12.5°, 18.5°, and 37.3°. Using Rigako software, an automatic background height determination without baseline smoothing was generated to determine the maximum peak heights at 12.5°, 18.5°, and 37.3°. The measured peak values ​​were ratioed. The results for Examples 1-10 are shown in Table 1.

[0098] Comparative Examples 1-5 were prepared by standard analytical stabilization procedures by reacting the same DLNO powder at room temperature without heat treatment with the same KOH / DLNO molar ratio and using pure water to form the mixture. Surprisingly, the battery materials obtained from these comparative examples had much higher gamma levels than the battery materials treated using the stabilization procedures described in this disclosure. Examples 1-10 were prepared using the stabilization procedures described in this disclosure.

[0099] Comparative Example 1 used the same DLNO powder as Example 1, but was prepared using the standard analytical stabilization procedure. As shown in Table 1, the KLDNO 12.5° / 37°(%) was 38.1%. In contrast, the stabilization procedure described in this disclosure reduced the KLDNO 12.5° / 37°(%) to 8.2% for Example 1 and 10.4% for Example 2.

[0100] Comparative Example 2 used the same DLNO powder as Example 3, but was prepared using a standard analytical stabilization procedure. As shown in Table 1, the KLDNO 12.5° / 37°(%) for Comparative Example 2 was 31.9%. In contrast, the stabilization procedure described in this disclosure reduced the KLDNO 12.5° / 37°(%) to 7.7% for Example 3 and 8.8% for Example 4.

[0101] Comparative Example 3 used the same DLNO powder as Example 5, but was prepared using the standard analytical stabilization procedure. As shown in Table 1, the KLDNO 12.5° / 37°(%) for Comparative Example 3 was 30.1%. In contrast, using the stabilization procedure described in this disclosure, the KLDNO 12.5° / 37°(%) was reduced to 9.9% for Example 5 and 10.0% for Example 6.

[0102] Comparative Example 4 used the same DLNO powder as Example 7, but was prepared using a standard analytical stabilization procedure. As shown in Table 1, the KLDNO 12.5° / 37°(%) for Comparative Example 4 was 87.3%. In contrast, the stabilization procedure described in this disclosure reduced the KLDNO 12.5° / 37°(%) to 12.0% for Example 7 and 16.2% for Example 8.

[0103] Comparative Example 5 used the same DLNO powder as Example 9, but was prepared using the standard analytical stabilization procedure. As shown in Table 1, the KLDNO 12.5° / 37°(%) for Comparative Example 5 was 118.1%. In contrast, the stabilization procedure described in this disclosure reduced the KLDNO 12.5° / 37°(%) to 15.4% for Example 9 and 17.6% for Example 10.

[0104] [Table 1]

Claims

1. 1. A method for preparing a battery material, comprising: Li ｘ Ni ｚ O ２ wherein x is in the range of about 0 to about 0.2 and z is in the range of about 0.1 to about 1, and the resulting mixture is mixed with an aqueous medium to form a Li ｘ Ni ｚ O ２ obtaining an aqueous suspension comprising: Li ｘ Ni ｚ O ２ heat-treating the aqueous suspension comprising: contacting the heat-treated suspension with an aqueous medium comprising an alkali, an alkaline earth hydroxide, KOH, or a combination thereof at a second temperature of about 20° C. to about 90° C. to produce a stabilized slurry comprising battery material solids and a filtrate, wherein the Li ｘ Ni ｚ O ２ the ratio of moles of hydroxide of alkali, alkaline earth hydroxide, KOH, or a combination thereof in said aqueous medium to moles of filtering the stabilized slurry to separate the solids from the filtrate. A method comprising:

2. The aqueous suspension is prepared by subjecting Li to a hypochlorite delithiation process. ｘ Ni ｚ O ２ The method of claim 1 , comprising:

3. the first heat treatment time is from about 30 minutes to about 120 minutes; and The method of claim 1, wherein the first heat treatment temperature is from about 50°C to about 90°C.

4. 10. The method of claim 1, wherein the first heat treatment time is from about 40 to about 80 minutes and the first heat treatment temperature is from about 65 to about 85°C.

5. 10. The method of claim 1, wherein contacting the heat-treated suspension with an aqueous medium comprising an alkali, an alkaline earth hydroxide, KOH, or a combination thereof at a second temperature is conducted for about 5 minutes to about 5 hours.

6. 10. The method of claim 1, wherein the temperature of the heat-treated suspension is altered prior to contacting the heat-treated suspension with the aqueous medium.

7. Li in the heat-treated suspension ｘ Ni ｚ O ２ 2. The method of claim 1, wherein the ratio of moles of hydroxide of alkali, alkaline earth hydroxide, KOH, or combination thereof in the aqueous medium to moles of ammonium hydroxide is from about 0.06 to about 0.

12.

8. 10. The method of claim 1, wherein the filtrate comprises from about 0% to about 5% by weight of KOH.

9. 10. The method of claim 1, wherein one or more of the aqueous medium and the aqueous suspension comprises regenerated filtrate.

10. The aqueous suspension contains about 10% to about 60% by weight of Li ｘ Ni ｚ O ２ The method of claim 1 , comprising:

11. 2. The method of claim 1, wherein the solid has a ratio of the maximum intensity count number at about 12.5° to the maximum intensity count number at about 37° of the solid, as measured by Cu-Kα powder X-ray diffraction analysis, of less than about 1.

0.

12. The method of claim 1 , wherein filtering the stabilized slurry comprises a pressure or vacuum filtration process.

13. 10. The method of claim 1, wherein the filter cake can be used unwashed or washed with water, weakly acidic water, or weakly caustic water.

14. 10. The method of claim 1, wherein the aqueous medium comprises alkali, alkaline earth hydroxide, KOH, or a combination thereof, at a concentration in the range of about 1% by weight or less, based on the total weight of the aqueous suspension.

15. At the start of the contacting step, Li ｘ Ni ｚ O ２ 10. The method of claim 1, wherein the material is present in an amount of 10% to 75% by weight based on the total weight of the suspension heat-treated in the aqueous medium.

16. 10. The method of claim 1, further comprising heat treating the solids separated from the filtrate for a second heat treatment time and a second heat treatment temperature.

17. 17. The method of claim 16, wherein the second heat treatment time ranges from about 30 minutes to about 24 hours.

18. 17. The method of claim 16, wherein the second heat treatment temperature ranges from about 50°C to about 100°C.

19. The method of claim 1 , wherein the battery material has an energy density in the range of about 300 mAh / g to about 400 mAh / g.

20. 10. The method of claim 1, wherein the battery material comprises about 0.5% to about 1.1% by weight of lithium, based on the total weight of the battery material, about 50% to about 70% by weight of nickel, based on the total weight of the battery material, and about 2% to about 6% by weight of potassium, based on the total weight of the battery material.

21. The solid after drying is about 1.8 g / cm ３ ~Approx. 2.5g / cm ３ 10. The method of claim 1, wherein the tap density is in the range of

22. Li ｘ Ni ｚ O ２ 10. The method of claim 1, further comprising a concentration of one or more of Co, Mn, Al, Mg, Ti, Zr, Nb, Hf, V, Cr, Sn, Cu, Mo, W, Fe, Si, Zn, B, other transition metals, rare earth elements, or combinations thereof, totaling less than about 5 wt.%.

23. 1. A method for preparing a battery material, comprising: Li ｘ Ni ｚ O ２ wherein x is in the range of about 0 to about 0.2 and z is in the range of about 0.1 to about 1, and the resulting mixture is mixed with an aqueous medium to form a Li ｘ Ni ｚ O ２ obtaining an aqueous suspension comprising: contacting the aqueous suspension with an aqueous medium comprising an alkali, an alkaline earth hydroxide, KOH, or a combination thereof at a second temperature of 20°C to 90°C to produce a stabilized slurry comprising battery material solids and a filtrate, wherein the Li in the heat-treated suspension is ｘ Ni ｚ O ２ the ratio of moles of hydroxide of alkali, alkaline earth hydroxide, KOH, or a combination thereof in said aqueous medium to moles of filtering the stabilized slurry to separate solids from the filtrate.

24. The aqueous suspension is prepared by adding Li derived from a hypochlorite desorption process. ｘ Ni ｚ O ２ 24. The method of claim 23, comprising:

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