Streamlined cathode battery material production process

Abstract

The present disclosure relates to a streamlined process for preparing cathode active materials (CAMs).

Description

STREAMLINED CATHODE BATTERY MATERIAL PRODUCTION PROCESS

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 603,252 filed on November 28, 2023, the entire contents of which are hereby incorporated by reference.FIELD OF THE INVENTION

[0002] The present invention relates to an improved and streamlined process for preparing cathode active materials (CAMs).BACKGROUND

[0003] Lithium-ion batteries (LiBs) are central to the ongoing transition to electric vehicles, driving advancements in technology, supporting renewable energy integration, and contributing to a more sustainable future. Their continued development will be key to addressing global energy challenges and achieving climate goals. The demand for LiBs is expected to grow to a large extent in several applications, particularly in connection with electric vehicles (EVs) over the coming years. Driven by rapid technological innovation, increasing environmental and energy concerns, favorable government policies, and growing demand from the renewable energy sector, this conversion is accelerating.

[0004] LiBs are typically classified into six major classifications depending on the chemical composition of the cathode material: (i) Lithium Nickel Manganese Cobalt Oxide (NMC), (ii) Lithium Nickel Cobalt Aluminum Oxide (NCA), (iii) Lithium Iron Phosphate (LFP), (iv) Lithium Cobalt Oxide (LCO), (v) Lithium Manganese Oxide (LMO), and (vi) Lithium Titanate (LTO).

[0005] Several methods have been explored and / or developed in the past 20 years for synthesizing the cathode material, including, e.g., solid-state reactions, sol -gel methods, coprecipitation, spray pyrolysis, and hydrothermal synthesis. Specifically, for the synthesis of NMC cathode material, the most common, hence current, method is co-precipitation of nickel(Ni), manganese (Mn), and cobalt (Co) to produce the single-phase precipitate, followed by solid-state reaction with a lithium (Li) compound.SUMMARY

[0006] Disclosed herein are improved and streamlined processes for the preparation of cathode active materials. The starting materials for any of the processes described herein may be, e.g., metal sulfates produced from processing ore, or a production stream obtained from recycling LiB (black mass).

[0007] The processes described herein provide one or more of the following advantages:(1) Improved homogenous mixing of the CAM precursors, for example, by (a) promoting better contact between lithium ions (Li+) and NMC particles creating a pre-lithiated structure, i.e., incorporation of Li1into the NMC structure leading to improved initial capacity, enhanced cycle life, and better overall efficiency, (b) promoting homogeneous and faster diffusion of Li during calcination, and (c) delivering consistent and optimal electrochemical performance of the CAM.(2) Lower processing and equipment costs, e.g., by minimizing the need, if not completely eliminating some intermediate steps (such as, e.g., in some aspects, a dry mixing step, and / or a doping step) and the corresponding equipment required for these steps before calcination.(3) Lower equipment costs by eliminating an additional processing system circuit for Li recovery and purification.

[0008] Any of the aspects of the present disclosure described herein may be combined.

[0009] In one aspect, the present disclosure relates to a process for preparing CAM.

[0010] In one aspect, the process includes:(a) providing a solution including one or more transition metal-containing CAM components and a Li compound in a solvent, optionally in the presence of one or more doping agents;(b) (i) co-precipitating the one or more transition metal-containing CAM components and the Li compound as hydroxides (e.g., by adding a hydroxide compound), or(ii) co-precipitating the one or more transition metal containing CAM components and the Li compound as carbonates (e.g., by adding a carbonate compound); where step (b) is conducted in the presence of a chelating agent.In one aspect, disclosed processes further includes:(c) isolating the co-precipitated product of step (b) (e.g., by filtration) and washing (with a medium such as, but not limited to, water, a detergent solution, ethanol, acetone, or any combination thereof) the co-precipitated product of step (b) (to remove one or more soluble impurities, such as ammonium hydroxide and / or sodium sulfate);(d) drying the product of step (c);(e) optionally, adding one or more doping agents to the product of step (d);(f) optionally, mixing (e.g., dry mixing) the product of step (d) or step (e) with one or more metal hydroxides and / or metal carbonates; and(g) calcining the product of step (d), step (e) if performed, or step (f) if performed.

[0011] In another aspect, step (e) is performed. In a further aspect, step (f) is performed. In another aspect, both step (e) and step (f) are performed. In another aspect, step (e) is not performed. In a further aspect, step (f) is not performed. In another aspect, both step (e) and step (f) are not performed. In another aspect of any of the methods described herein, the one or more transition metal- containing CAM components include compounds containing Ni, Mn, Co,aluminum (Al), iron (Fe), titanium (Ti), and any combination of any of the foregoing, depending on the desired cathode chemistry.

[0012] In one aspect of any of the methods described herein, the one or more transition metal- containing CAM components are transition metal sulfate salts, or hydrates thereof. For example, in one aspect of any of the methods described herein, in a process for the preparation of NMC, the one or more transition metal containing CAM components include nickel sulfate hexahydrate (NiSCkbFFO), manganese sulfate monohydrate (MnSCUFfcO), and cobalt sulfate heptahydrate (COSO4.7H2O).

[0013] In one aspect of any of the methods described herein, the CAM includes lithium nickel manganese cobalt oxide (i.e., the CAM is NMC). In one aspect of any of the methods described herein, the CAM includes lithium nickel cobalt aluminum oxide (i.e., the CAM is NCA). In one aspect of any of the methods described herein, the CAM includes lithium iron phosphate (i.e., the CAM is LFP). In one aspect of any of the methods described herein, the CAM includes lithium cobalt oxide (i.e., the CAM is LCO). In one aspect of any of the methods described herein, the CAM includes lithium manganese oxide (i.e., the CAM is LMO). In one aspect of any of the methods described herein, the CAM includes lithium titanate (i.e., the CAM is LTO). In one aspect of any of the methods described herein, the Li compound is selected from, but not limited to, lithium carbonate (LisCCh), lithium hydroxide (LiOH), lithium sulfate (LiSCh), lithium oxide (LizO), and any combination thereof.

[0014] In one aspect of any of the methods described herein, the hydroxide compound used in step (b)(i) is an alkali metal hydroxide, an alkali earth metal hydroxide, or any combination thereof. Suitable examples of hydroxide compounds include, but are not limited to, sodium hydroxide (NaOH), potassium hydroxide (KOH), LiOH, and any combination thereof.

[0015] In one aspect of any of the methods described herein, the carbonate compound used in step (b)(ii) is a soluble carbonate compound, such as, for example, an alkali metal carbonate, an alkali earth metal carbonate, an ammonium carbonate, or any combination thereof. Suitable examples of carbonate compound include, but are not limited to, sodium carbonate (Na2COs), potassium carbonate (K2CO3), sodium bicarbonate (NaHCCh), ammonium carbonate ((NHFLCCh), ammonium bicarbonate (NH4HCO3), and any combination thereof.

[0016] In one aspect of any of the methods described herein, the chelating agent (also referred to interchangeably herein as complexing agent) is selected from, but not limited to, ammonia (NH3), ammonium hydroxide (NH4OH), ethylene diamine tetraacetic acid (EDTA), citric acid (CeHsCh), and any combination thereof.

[0017] In one aspect of any of the methods described herein, when the one or more transition metal-containing CAM components are metal sulfates salts, step (a) includes mixing the one or more metal sulfate salts and the Li compound in water. In one non-limiting aspect, the metal sulfate salts include Ni sulfate, Mn sulfate and Co sulfate salts. In another aspect of any of the methods described herein, when the one or more transition metal-containing CAM components is a solution obtained from a LiB recycling process, step (a) includes mixing the solution obtained from the LiB recycling process with the Li compound.

[0018] In one aspect of any of the methods described herein, step (b)(i) is conducted at a pH of between about 10 and about 12, such as between about 10.5 and about 12, or between about 10.2 and about 10.8. In one aspect, step (b)(i) is conducted at a pH of about 10, about 10.5, about 11, about 11.5 or about 12.

[0019] In one aspect of any of the methods described herein, step (b)(i) is conducted at a temperature of between about 30 °C and about 80 °C, such as between about 50 °C and about 60 °C

[0020] In one aspect of any of the methods described herein, step (b)(ii) is conducted at a pH of between about 7 and about 10, such as between about 7 and about 9.5. In one aspect, step (b)(ii) is conducted at a pH of about 7, about 7.5, about 8, about 8.5, about 9, about 9.5 or about 10.

[0021] In one aspect of any of the methods described herein, step (b)(ii) is conducted at a temperature of between about 30 °C and about 80 °C, such as between about 50 °C and about 60

[0022] In one aspect of any of the methods described herein, the one or more transition metal-containing CAM components, and the lithium compound used in step (a) are purified saltsproduced from processing of ores. In one aspect of any of the methods described herein, the one or more transition metal -containing CAM components and the lithium compound used in step (a) are recovered from a pregnant leach solution (PLS) generated from the recycling of LiB waste. See, e.g., Example 3.

[0023] In another aspect, the present invention relates to a process for preparing CAM, the process including:(a)(i) mixing Ni sulfate, Mn sulfate and Co sulfate salts with a Li compound in water to form a solution, optionally in in the presence of one or more doping agents, or(ii) mixing a solution obtained from LiB recycling including Ni, Mn and Co, with a Li compound, optionally in in the presence of one or more doping agents; and(b)(i) co-precipitating the product of step (a)(i) or (a)(ii) as hydroxides (e.g., by adding a hydroxide compound), or(ii) co-precipitating the product of step (a)(i) or (a)(ii) as carbonates (e.g., by adding a carbonate compound); where step (b) is conducted in the presence of a chelating agent.In one aspect, the process further includes:(c) isolating the co-precipitated product of step (b) (e.g., by filtration) and washing (with medium such as, but not limited to, water, detergent solution, ethanol, acetone, or any combination thereof) the co-precipitated product of step(b) (to remove one or more soluble impurities, such as ammonium hydroxide and / or sodium sulfate);(d) drying the product of step (c);(e) optionally, adding one or more doping agents to the product of step (d);(f) optionally, mixing (e.g., dry mixing) the product of step (d) or step (e) with one or more metal hydroxides and / or carbonates; and(g) calcining the product of step (d), step (e) if performed, or step (f) if performed.

[0024] In one aspect of any of the methods described herein, one or more doping agents may be selected from, but not limited to, one or more compounds containing Al, Mg, Zr, Ti, or any combination thereof. In one aspect of any of the methods described herein, the one or more metal hydroxides and / or carbonates optionally added in step (f) may be selected from, but not limited to, one or more hydroxides and / or carbonates containing Ni, Mn, Co, Li, or any combination thereof.

[0025] In one aspect, step (e) is performed. In a further aspect, step (f) is performed. In another aspect, both step (e) and step (f) are performed. In one aspect, step (e) is not performed. In a further aspect, step (I) is not performed. In another aspect, both step (e) and step (f) are not performed. In one aspect of any of the methods described herein, the process does not involve a separate Li recovery step.BRIEF DESCRIPTION OF THE DRAWINGS

[0026] FIG. 1 is an exemplary process flow diagram showing a process for preparing a NMC CAM, performed in accordance with current industry practice.

[0027] FIG. 2 is an exemplary process flow diagram showing a process for preparing a NMC CAM, performed according to one aspect as described herein. It will be understood that the process shown in FIG. 2 is only illustrative and is non-limiting. Additional process steps to those shown may be added (or removed) as required.

[0028] FIG. 3 is an exemplary process flow diagram showing a process for preparing a NMC CAM, performed according to one aspect as described herein. It will be understood that the process shown in FIG. 3 is only illustrative and is non-limiting. Additional process steps to those shown may be added (or removed) as required.DETAILED DESCRIPTION

[0029] The conventional CAM production method currently employed in the industry is the solid-state method that involves the reaction of a NMC precursor and a Li compound. This process involves a series of steps, including doping, mixing, and milling. These extra process steps result in high capital and operating costs. In addition, Li compounds, especially LiOH, are highly hygroscopic, and tend to form larger particles by agglomeration, requiring the agglomerated particles to be milled prior to mixing with the NMC. In the process of milling, the milled lithium particles (such as LiOH) become non-uniform and elongated. Mixing such non- uniform and elongated particles with uniformly sized and spherical NMC particles results in an undesirable heterogeneous distribution. It also can result in contact problems, where some particles may be under-lithiated and some particles may be over-lithiated, which ultimately negatively affects battery performance.

[0030] Malik et al., Materials Energy Today, 28, 101066, 2022, provides a review on the synthesis of LiNixMnyCoi-x-yO2 (NMC) cathodes for lithium-ion batteries. This solid-state method is industrially employed for the ease at which the correct stoichiometric mix of Li and NMC may be achieved. However, it suffers some drawbacks. For example, this method requires significant and efficient mechanical mixing of the Li and NMC precursors to ensure homogeneity of contact between and distribution of particles. In some cases, where milling is employed in conjunction with mixing, wide particle size distribution, agglomeration of fine particles, and particle structure degradation due to mechanical stress may present additional issues.

[0031] U.S. Patent No. 7,488,465 describes the solid-state synthesis of lithium-ion battery cathode materials, and the application of wet milling techniques in producing singlephase Li and transition metal compounds. In this method, Ni-, Co-, Mn-, and Li-containing oxides or oxide precursors are mixed to form a finely divided slurry, followed by heating theslurry to form a solid solution. The synthesis requires elevated temperatures to facilitate the formation of a solid solution, which can lead to energy-intensive processes and may cause degradation of sensitive components such as Li. Achieving a uniform solid solution can also be challenging as variability in the process may result in phase separation or the formation of undesirable secondary phases. In addition, wet milling is a more extensive and complex process compared to dry milling.

[0032] A paper by Nguyen et al. published online in 2024 (“An Evaluation of All-Dry, Zero-Waste Cathode Synthesis Technology onMid-Nickel LiNio.6Mno.2Coo.2O2 (NMC622) at the Pilot Scale, ” https: / / www.novonixgroup.com) describes an evaluation of an all-dry zero-waste cathode synthesis technology on mid-nickel LiNio.6Mno.2Coo.2O2 (NMC622) and references Japanese Patent No. JP 7504195. In this technology, transition metal feed materials in forms such as metallic, oxide, carbonate, or combinations thereof, are mixed with Li2C0.3 or LiOH, then calcined under an O2 atmosphere. The resulting calcined material undergoes primary crushing using a roller crusher followed by fine grinding using a jet mill. Relative to the conventional CAM production process described above, the addition of jet milling is an additional and expensive step. It also requires significant energy input, leading to higher operational costs, especially at larger scales. The high-velocity impacts involved in jet milling can cause wear and tear on equipment, necessitating frequent maintenance and replacement of parts, which also increases cost. The process can also produce fine dust, which may pose safety hazards and require additional dust collection systems to manage. It can also potentially cause iron contamination, depending on materials of construction, operation, and maintenance. Furthermore, as discussed above, the traditional solid-state method for reacting Li and NMC precursors experiences issues with inhomogeneity, which are even more pronounced when reacting four components.

[0033] International Publication No. WO 2018 / 132903 describes a one pot synthesis for lithium-ion battery cathode material precursors. In the process, starting material metal carbonates in water, and mixed with a carboxylic acid, such as oxalic acid. Simultaneous leaching of the metals and their precipitation (e.g., as oxalate compounds) occur. To achieve the desired pH, NH4OH may be used to increase the pH (with LiOH being preferred), and formic acid may be used to decrease the pH. The entire slurry is then fed into a spray dryer at 300-350° C producingfine, ultrafine, or nanosized particles, and then calcined at 900° C. As all components react simultaneously, achieving optimal reaction conditions (temperature, pH, and time) can be challenging, which may lead to variability in the final product. It is also less versatile in accommodating a wide range of precursor materials compared to the conventional synthesis methods. With regards to the use of oxalic acid, the use of this reagent makes the process more costly because it is decomposed in the process, hence, unrecoverable for reuse. From a cost perspective, spray drying requires expensive equipment and complex operational controls to maintain optimal conditions. Additionally, oxalic acid is highly toxic and corrosive and poses significant safety and environmental risks.

[0034] In yet another entirely different method aimed at streamlining the CAM production process, the sol-gel route has been studied. The sol-gel method involves the dissolution of metal precursors, such as nitrates or alkoxides, in a solvent to create a homogeneous sol. This sol then undergoes hydrolysis and condensation reactions to form a gel, which is subsequently dried to produce a xerogel. The xerogel is then calcined at high temperatures to convert it into the desired crystalline phase, such as NMC or LFP. Such procedures are described in, e.g., Smith et.al. (Chapter 36) of The Sol-Gel Handbook: Synthesis, Characterization and Applications, 1stEd., Levy & Zayat (Eds.), Wiley, 2017, and Etacheri el al. (Chapter 6) of Sol-Gel Materials for Energy, Environment and Electronic applications, Advances in Sol-Gel Derived Materials and Technologies, Pillai & Hehir (Eds.), Spring International Publishing, 2017. Such sol -gel methods have not yet found their way into commercial applications. One of the main issues associated with this sol-gel method is that it requires sophisticated manufacturing procedures, releases toxic NOx gases during synthesis, and the use of non-recoverable organic compounds. Moreover, the operational process of this route is comparatively more complex, requiring a long preparation time, having greater environmental contamination, and hence, leading to high energy consumption and high production cost.

[0035] There is a need for new methods for the preparation of CAM that improves upon the drawbacks discussed herein. The present disclosure addresses these needs.

[0036] As used herein the term “about” means an acceptable error for a particular value as determined by one of ordinary skill in the art, which depends in part on how the value ismeasured or determined. In certain aspects, the term “about” means within 1, 2, 3, or 4 standard deviations. In certain aspects, the term “about” means within 15%, 10%, 9%, 8%, 7%, 6%, 5%,4%, 3%, 2%, 1%, 0.5%, or 0.05% of a given value or range.

[0037] As used herein, the term “comprising” (and related terms such as “comprise” or “comprises” or “having” or “including”) includes, but is not limited to, those embodiments, for example, an embodiment of any composition of matter, composition, method, or process, or the like, that “consist of’ or “consist essentially of’ the described features.

[0038] All ranges disclosed herein are inclusive of the recited endpoint and independently combinable (for example, the range of “from 2 to 10” is inclusive of the endpoints, 2 and 10, and all the intermediate values). The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value; they are sufficiently imprecise to include values approximating these ranges and / or values. As used herein, approximating language may be applied to modify any quantitative representation that may vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about,” may not be limited to the precise value specified, in some cases. In at least some instances, the approximating language may correspond to the precision of an instrument for measuring the value. The modifier “about” should also be considered as disclosing the range defined by the absolute values of the two endpoints. For example, the expression “from about 2 to about 4” also discloses the range “from 2 to 4.” The term “about” may refer to plus or minus 10% of the indicated number. For example, “about 10%” may indicate a range of 9% to 11”, and “about 1” may mean from 0.9-1.1. Other meanings of “about” may be apparent from the context, such as rounding off, so, for example “about 1” may also mean from 0.5 to 1.4.

[0039] When amounts, concentrations, dimensions and other parameters are expressed in the form of a range, a preferable range, an upper limit value, a lower limit value or preferable upper and limit values, it should be understood that any ranges obtainable by combining any upper limit or preferable value with any lower limit or preferable value are also specifically disclosed, irrespective of whether the obtained ranges are clearly mentioned in the context.

[0040] In one embodiment of the processes described herein, a solution containing the sulfates of Ni, Mn, and Co and a suitable Li compound such as, but not limited to, Li2CCh, LiOH, and Li2SO4, proceeds to a co-precipitation step where Ni, Mn, Co, and Li are all coprecipitated. Relative to a previously known conventional process, the intermediate steps and corresponding equipment between pCAM and CAM production such as separate Li recovery process steps, doping, and mixing may be eliminated. When the same is integrated in the hydrometallurgical recycling process for LiB waste, the whole process becomes closed loop, which allows for high recovery of Ni, Mn, Co and Li.

[0041] FIG. 1 is an exemplary process flow diagram showing a process for preparing a NMC CAM performed in accordance with current industry practice.

[0042] The current industry practice process of FIG.1 involves providing a solution containing Ni, Mn and Co sulfates (10). A chelating agent (20) and a sodium compound (such as NaOH or Na2COs) acting as precipitating agent (30) are added, and the Ni, Mn and Co are coprecipitated (S100). The co-precipitated Ni, Mn and Co product is filtered and washed (S200) with a washing medium (40). The filtrate and washings (50) may be treated and discharged. The resulting co-precipitated product is then dried (S300). Doping agents (60) may be added in a doping step (S400). A Li compound (such as LiOH or Li2(COa)) (70) is then added and the Li- NMC product mixed (S500). A calcination step (S600) is then performed to produce the NMC CAM product (80).

[0043] FIG. 2 is an exemplary process flow diagram showing a process for preparing a NMC CAM according to a non-limiting aspect as described herein.

[0044] The non-limiting process of FIG. 2 involves providing a solution containing Ni, Mn and Co sulfates (11). A Li compound (such as LiOH or Li2(CO3)) acting as Li source and precipitating agent (21), optionally with a sodium compound (such as NaOH or Na2CO3) acting as a precipitating agent (51), and a chelating agent (31) and, optionally, one or more doping agents (41) are added, and the Ni, Mn, Co and Li are co-precipitated as hydroxides and / or as carbonates (S101). The co-precipitated Ni, Mn, Co and Li product is filtered and washed (S201) with a washing medium (61). The filtrate and washings (71) may be treated and discharged. The resulting co-precipitated product is then dried (S301). Optionally, adjustment of the finalcomposition may be made (e.g., varying the Li and NMC ratios) by adding one or more metal hydroxides and / or metal carbonates (91) via an optional dry mixing step. One or more doping agents (81) may optionally also be added. A calcination step (S401) is then performed to produce the NMC CAM product (101).

[0045] FIG. 3 is another exemplary process flow diagram showing a process for preparing a NMC CAM according to a non-limiting aspect as described herein.

[0046] The non-limiting process of FIG. 3 involves providing a solution containing Ni, Mn and Co sulfates (11). A Li compound (such as Li OH or Li2(CO3)) acting as Li source and precipitating agent (21), optionally with a sodium compound (such as NaOH or Na2COa) acting as a precipitating agent (51), and a chelating agent (31) and, optionally, one or more doping agents (41) are added, and the Ni, Mn, Co and Li are co-precipitated as hydroxides and / or as carbonates (S101). The co-precipitated Ni, Mn, Co and Li product is filtered and washed (S201) with a washing medium (61). The filtrate and washings (71) may be treated and discharged. The resulting co-precipitated product is then dried (S301). One or more doping agents (81) may optionally also be added. Adjustment of the final composition is made (e.g., varying the Li and NMC ratios) by adding one or more metal hydroxides and / or carbonates (91) via a dry mixing step (S401). A calcination step (S501) is then performed to produce the NMC CAM product (101)

[0047] The present invention will now be described by the following non-limiting examples.EXAMPLESExample 1 - Co-Precipitation via the Carbonate Route

[0048] A solution containing Ni, Mn, Co as sulfates and one or more Li containing compounds (such as, but not limited to, Li2CO3) is added, with or without additional doping agents (such as, but not limited to compounds containing Al, Mg, Zr, and Ti) to the same reactor. Then, the Ni, Mn, Co, and Li are precipitated as carbonates (e.g., at a pH of about 7 to about 9.5) by adding a soluble carbonate, such as, but not limited to, Li2CO3,Na2CO3, (NH^CCh, K2CO3,and NaHCOi, in the presence of a chelating agent (such as, but not limited to, NH4OH) under conditions known in the art. The Li-NMC carbonate product thus formed is fdtered and washed using conditions known in the art to remove soluble impurities, such as, e.g., ammonium hydroxide and sodium sulfate. The washed Li-NMC product is then dried and calcined.Example 2 - Co-Precipitation via the Hydroxide Route

[0049] A solution containing Ni, Mn, Co as sulfates, and one or more Li containing compounds (such as, but not limited to, LiOH) is added, with or without additional doping agents (such as, but not limited to compounds containing Al, Mg, Zr, and Ti) to the same reactor. Then, the Ni, Mn, Co, and Li are precipitated as hydroxides (e.g., at a pH of about 10.5 to about 12) by adding an alkali hydroxide such as, but not limited to, NaOH, KOH, and LiOH, in the presence of a chelating agent (such as, but not limited to, NH4OH) under conditions known in the art. The Li-NMC hydroxide product thus formed is filtered and washed using conditions known in the art to remove soluble impurities, such as, e.g., ammonium hydroxide and sodium sulfate. The washed Li-NMC product is then dried and calcined.Example 3 - Production of NMC from PLS Generated from the Recycling of LiB Waste

[0050] A solution containing Ni, Mn, Co as sulfates, and one or more Li containing compounds (such as, but not limited to, LiOH or LizCOs) is added, with or without additional doping agents (such as, but not limited to compounds containing Al, Mg, Zr, and Ti) to the same reactor. Then, the Ni, Mn, Co, and Li are precipitated as hydroxides (e.g., at a pH of about 11) by adding an alkali hydroxide such as, but not limited to, NaOH, KOH, and LiOH, or as carbonates (e g. at a pH of about 9) by adding an alkali carbonate such as, but not limited to, Na2CO3, (TML hCOa, K2CO3, and NaHCOs, in the presence of a chelating agent (such as, but not limited to, NH4OH) under conditions known in the art. After an optimum reaction time, corresponding to the time required for formation of the desired NMC particle size and morphology, the Li in solution may be precipitated as LiOH or Li2CO . The extent of precipitation of Li may be controlled such that its composition in the final product is equivalent to one mole per mole of NMC. The slurry product thus formed may be filtered and washed to remove soluble impurities, such as, e.g., ammonium hydroxide and sulfates.

[0051] All patents and publications cited herein are incorporated by reference in their entirety.

Claims

WHAT IS CLAIMED IS:

1. A process for preparing a cathode active material (CAM), the process comprising:(a) providing a solution comprising one or more transition metal-containing CAM components and a Li compound in a solvent, optionally in the presence of one or more doping agents; and,(b) (i) adding a hydroxide compound thereby co-precipitating the one or more transition metal-containing CAM components and the Li compound as hydroxides as a co-precipitated product, or(ii) adding a carbonate compound thereby co-precipitating the one or more transition metal-containing CAM components and the Li compound as carbonates as a co-precipitated product; wherein step (b) is conducted in the presence of a chelating agent.

2. The process of claim 1, further comprising:(c) isolating the co-precipitated product of step (b) and washing the coprecipitated product of step (b);(d) drying the washed product of step (c);(e) optionally, adding one or more doping agents to the product of step (d);(f) optionally, mixing the product of step (d) or step (e) with one or more metal hydroxide and / or metal carbonate; and(g) calcining the product of step (d), step (e) if performed, or step (f) if performed.

3. The process of claim 1 or claim 2, wherein the Li compound is selected from the group consisting of Li2CCh, LiOH, LiSCU, Li2O, and any combination thereof.

4. The process of any one of claims 1-3, wherein in step (b)(i) the hydroxide compound is selected from the group consisting of an alkali metal hydroxide, an alkali earth metal hydroxide, and any combination thereof.

5. The process of any one of claims 1-4, wherein in step (b)(i) the hydroxide compound is selected from the group consisting of NaOH, KOH, LiOH, and any combination thereof.

6. The process of any one of claims 1-3, wherein in step (b)(ii) the carbonate compound is selected from the group consisting of an alkali metal carbonate, an alkali earth metal carbonate, an ammonium carbonate, and any combination thereof.

7. The process of any one of claims 1-3 and 6, wherein in step (b)(ii) the carbonate compound is selected from the group consisting of Na2CCh, K2CO3, NaHCCh, (NH^CCh, NH4HCO3, and any combination thereof.

8. The process of any one of claims 1-7, wherein the chelating agent is selected from the group consisting of NH3, NH4OH, ethylene diamine tetraacetic acid (EDTA), citric acid (CeHsO?), and any combination thereof.

9. The process of any one of claims 1-8, wherein step (b)(i) is conducted at a pH of between about 10 and about 12.

10. The process of any one of claims 1-8, wherein step (b)(ii) is conducted at a pH of between about 7 and about 10.11 . The process of any one of claims 1-10, wherein step (b) is conducted at a temperature of between about 30 °C and about 80 °C.

12. A process for preparing CAM, the process comprising:(a)(i) mixing Ni sulfate, Mn sulfate and Co sulfate with a Li compound in water to form a solution, optionally in in the presence of one or more doping agents, or(ii) mixing a solution obtained from LiB recycling comprising nickel, manganese and cobalt, with a Li compound, optionally in in the presence of one or more doping agents; and(b)(i) adding a hydroxide compound thereby co-precipitating the product of step (a)(i) or (a)(ii) as hydroxides as a co-precipitated product, or(ii) adding a carbonate compound thereby co-precipitating the product of step (a)(i) or (a)(ii) as carbonates as a co-precipitated product; wherein step (b) is conducted in the presence of a chelating agent.

13. The process of claim 12, further comprising:(c) isolating the co-precipitated product of step (b) and washing the coprecipitated product of step (b);(d) drying the product of step (c);(e) optionally, adding one or more doping agents to the product of step (d);(f) optionally, mixing the product of step (d) or step (e) with one or more metal hydroxide and / or metal carbonate; and(g) calcining the product of step (d), step (e) if performed, or step (f) if performed.

14. The process of claim 12 or claim 13, wherein the Li compound is selected from the group consisting of Li2C0.3, LiOH, LiSCU, Li2O, and any combination thereof.

15. The process of any one of claims 12-14, wherein the hydroxide compound used in step (b)(i) is an alkali metal hydroxide, an alkali earth metal hydroxide, or any combination thereof.

16. The process of any one of claims 12-15, wherein the hydroxide compound used in step (b)(i) is selected from the group consisting of NaOH, KOH, LiOH, and any combination thereof.

17. The process of any one of claims 12-14, wherein the carbonate compound used in step (b)(ii) is an alkali metal carbonate, an alkali earth metal carbonate, an ammonium carbonate, or any combination thereof.

18. The process of any one of claims 12-14 and 17, wherein the carbonate compound used in step (b)(ii) is selected from the group consisting of Na2COs, K2CO3, NaHCCh, (NH4)2CO3, NH4HCO3, and any combination thereof.

19. The process of any one of claims 12-18, wherein the chelating agent is selected from the group consisting of NH3, NH4OH, ethylene diamine tetraacetic acid (EDTA), citric acid (CeHsO?), and any combination thereof.

20. The process of any one of claims 12-19, wherein step (b)(i) is conducted at a pH of between about 10 and about 12.

21. The process of any one of claims 12-19, wherein step (b)(ii) is conducted at a pH of between about 7 and about 10.

22. The process of any one of claims 12-21, wherein step (b) is conducted at a temperature of between about 30 °C and about 80 °C.

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