Method for purifying and precipitating materials from batteries for recycling and manufacturing processes

Abstract

The present disclosure relates to systems and methods for recovering one or more nickel-containing products from battery manufacturing scrap materials and producing a lithium sulfate solution with improved by-products and minimal waste streams. In particular, in one or more embodiments, the disclosed methods may include leaching the battery manufacturing scrap materials in an acidic solution to produce a metal-containing solution. Further, the methods may process the metal-containing solution to recover one or more nickel-containing products and produce a lithium sulfate solution. Further, the methods may evaporate the lithium sulfate solution to produce lithium sulfate (LiSO).

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of and priority to U.S. Provisional Patent Application No. 63 / 440,281, entitled "Purification and Precipitation Methods for Battery Recycling and Manufacturing Processes," filed January 20, 2023. The aforementioned patent application is incorporated herein by reference in its entirety. [Background technology]

[0002] The development of the global economy and urban transportation has led to increasing oil depletion and environmental pollution. In response, many developed countries around the world are racing to develop green energy technologies. Among them, the power generation sector, represented by the application of electric vehicles, is growing most rapidly. In fact, electric vehicles are the key to replacing fuel-powered vehicles and their associated negative impacts.

[0003] Due to the low energy storage capacity, heavy weight, short lifespan, and danger of traditional chemical batteries, battery production has become a bottleneck in the industrialization of electric vehicles. The utilization rate of lithium batteries in electric vehicles has increased significantly. Lithium-ion batteries are likely to become the mainstream power supply route for future electric vehicles, so there is ample room for development and growth in the lithium battery industry.

[0004] With the widespread application of lithium-ion batteries as power sources for electric vehicles, how to recycle used lithium-ion batteries and how to recycle resources has become a general concern in society. For the sake of resource recycling and the sustainable development of industry, valuable battery metals should be recycled.

[0005] In recent years, there has been significant interest in improving battery recycling systems. For example, conventional systems involve the production of costly and minimally useful by-products. For example, conventional systems often produce by-products such as sodium sulfate, which can be problematic when recovering metals from recycled batteries. Furthermore, conventional systems often produce waste streams that must be heavily treated before they can be discharged or before their components can be reused.

[0006] These and additional problems and challenges exist with conventional battery recycling systems. Summary of the Invention [Means for solving the problem]

[0007] Embodiments of the present disclosure provide benefits and / or solve one or more of the aforementioned or other problems in the art through methods for recovering battery materials from battery manufacturing scrap materials with improved by-products and minimal waste streams. In particular, the methods can include recovering valuable metals from battery manufacturing scrap and producing products important to battery manufacturing and recycling through various processes including mechanical separation, acid leaching, precipitation, electrolysis, oxidation, precipitation, etc.

[0008] For example, the method may include recovering metals such as aluminum, iron, and copper from battery manufacturing scrap materials through mechanical separation. Furthermore, as part of the lithium recovery process, one or more embodiments include producing a stream containing lithium and other metals via one or more acid leaching processes. Furthermore, the method may include performing different levels of processing to recover different forms of nickel-containing products from the metal-containing stream. For example, one or more embodiments include recovering the nickel-containing product in the form of a hydrogen metal concentrate (e.g., a composite product containing a high-nickel concentrate, a mixed hydroxide precipitate (MHP), and gypsum). One or more alternative embodiments include recovering the nickel-containing product in the form of a high-nickel concentrate and a separate composite MHP and gypsum product. Furthermore, the MHP and gypsum may be separated in one or more embodiments. Further embodiments include producing mixed metal sulfates (MMS) through evaporation and crystallization. Furthermore, the method may include purifying the MMS to make it suitable feed for pCAM without further purification. Additionally or alternatively, the systems and methods can include precipitating additional base metals from the MMS through the addition of calcium-based products such as lime, thereby separating these metals from the lithium without producing sodium sulfate by-product. Further, various embodiments include recovering lithium in addition to the nickel-containing product, resulting in improved by-products and minimized waste streams.

[0009] Additional features and advantages of one or more embodiments of the present disclosure will be set forth in the description that follows, and in part will be obvious from the description, or may be learned by practice of such exemplary embodiments. [Brief explanation of the drawings]

[0010] The detailed description provides additional specificity and detail to one or more embodiments through the use of the accompanying drawings, as briefly described below. [Figure 1]1 illustrates a process for recovering Ni-containing products and lithium sulfate (LiSO) from battery manufacturing scrap materials, according to one or more embodiments. [Figure 2] 1 illustrates a process for recovering hydrogen metal concentrate and Li2SO4 from battery manufacturing scrap materials, according to one or more embodiments. [Figure 3] 1 illustrates a process for recovering high nickel concentrate and i2SO4 from battery manufacturing scrap materials, according to one or more embodiments. [Figure 4] 1 illustrates a process for recovering MMS and Li2SO4 from battery manufacturing scrap materials, according to one or more embodiments. [Figure 5] 1 illustrates an exemplary series of operations for recovering battery materials from battery manufacturing scrap materials with improved by-products and minimal waste streams, according to one or more embodiments. [Figure 6] 1 illustrates another exemplary series of operations for recovering battery materials from battery manufacturing scrap materials with improved by-products and minimal waste streams, according to one or more embodiments. [Figure 7] 1 illustrates yet another exemplary series of operations for recovering battery materials from battery manufacturing scrap materials with improved by-products and minimal waste streams, according to one or more embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present disclosure describes one or more embodiments of a method for recovering battery metals, including lithium, from battery manufacturing scrap materials and converting the lithium to battery-grade lithium hydroxide (LiOH) or lithium sulfate monohydrate with improved by-products and minimal waste streams. More specifically, the method can include recovering valuable metals from battery manufacturing scrap materials and producing products important for battery manufacturing and recycling through various processes, including mechanical separation, acid leaching, precipitation, electrolysis, oxidation, precipitation, etc. One or more embodiments include one of two leaching processes. Specifically, in one or more embodiments, the first leaching process includes a sulfuric acid leaching conducted to selectively recover lithium over nickel and cobalt into solution. The second leaching process includes a sulfuric acid leaching conducted with peroxide addition to maximize the recovery of lithium, nickel, and cobalt into solution. In the first leaching process, minimal processing, complexity, and cost are required to recover lithium from the feed and render the nickel and cobalt into desirable forms for further purification. In the second leaching process, more intensive treatment is applied in the leaching stage through the addition of peroxide or other reducing agents to leach nearly all of the nickel, cobalt, and lithium into solution, with the majority of the nickel and cobalt being recovered in the form of metal sulfates that can be easily integrated into pCAM operations after purification of the metal sulfates. In both cases, the lithium is separated from the nickel and cobalt for recovery as lithium sulfate and optionally converted to lithium hydroxide.

[0012] More specifically, one or more embodiments include recovering metals such as aluminum (Al), iron (Fe), and copper (Cu) from cathode and anode electrode powders (e.g., cathode active material and graphite) through a mechanical separation process. Furthermore, as part of the lithium recovery process, one or more embodiments include generating a stream containing lithium and other metals via one or more acid leaching processes. One or more embodiments described herein address the challenge of separating the remaining metals in solution from the lithium so that the lithium can be recovered and optionally converted to LiOH. Furthermore, one or more embodiments described herein separate the remaining metals in solution from the lithium without producing sodium sulfate by-product, which is expensive to manage because sodium sulfate must be crystallized in two stages to separate it from the lithium, and the final product may not be commercial grade. Indeed, one or more embodiments described herein separate the remaining metals in solution from the lithium without precipitation using a sodium-based alkali, such as sodium hydroxide, to avoid the production of sodium sulfate, as is done by conventional processes.

[0013] One or more implementations recover the nickel-containing product in one or more different forms depending on the desired end use of the recovered material or the desired processing efficiency / process. Various implementation embodiments include performing different levels of processing to recover the nickel-containing product in different forms. For example, one or more embodiments include recovering the nickel-containing product in the form of a hydrogen metal concentrate (e.g., a composite product containing high nickel concentrate, mixed hydroxide precipitate (MHP), and gypsum) from battery manufacturing scrap material. For example, the method includes acid leaching (e.g., without peroxide) the battery manufacturing scrap material to selectively leach lithium with high efficiency while leaching Ni with lower efficiency. The leaching process produces a metal-containing stream. Furthermore, in some embodiments, the method includes treating the metal-containing stream to recover a hydrogen metal concentrate. Specifically, in one or more implementations, the method includes precipitating metals from the stream by adding a calcium-based product (e.g., lime) and filtering the stream to recover the hydrogen metal concentrate. Producing a hydrogen metal concentrate requires fewer processing steps and results in a more efficient process, but can result in a relatively crude and unpurified product while still leaving the lithium in solution for recovery in subsequent processes.

[0014] One or more alternative embodiments include recovering the nickel-containing product from the stream in the form of a high-nickel concentrate and a separate but combined MHP and gypsum product. Specifically, such embodiments include filtering the high-nickel concentrate from a metals-containing stream resulting from acid leaching (e.g., without peroxide) of mechanically separated battery manufacturing materials. For example, the method can include passing the metals-containing stream to a filter tank and then filtering the stream using a filter aid, such as diatomaceous earth (DE). In one or more embodiments, filtering the metals-containing stream through the filter aid provides a clear filtrate and a filter cake suitable for transportation (i.e., a high-nickel concentrate). Furthermore, in one or more embodiments, the method includes separating lithium in the resulting filtrate from other metals (e.g., Ni, Co, and Al) by precipitating the metals with a calcium-based product (e.g., hydrated lime) using a method similar to that described above, thereby obtaining a combined MHP and gypsum product. In such implementations, the gypsum may be further separated from the MHP or may remain in the combined MHP and gypsum product. Recovering a high nickel concentrate and a separate but combined MHP and gypsum product requires more processing steps than producing a hydrogen metal concentrate, but results in a more refined product.

[0015] Further embodiments include producing mixed metal sulfates (MMS) from a metal-containing stream by evaporation and crystallization. Furthermore, the method can include purifying the MMS and utilizing it as a suitable feed for pCAM without further purification from MMS purification. Additionally, or alternatively, the system and method can include precipitating additional base metals from MMS through the addition of a calcium-based product, such as lime, thereby separating these metals from lithium without producing a sodium sulfate by-product. In one or more embodiments, the method can produce MMS of nickel (Ni), manganese (Mn), and cobalt (Co). The method can produce MMS by evaporation and optional crystallization of a metal-containing filtrate obtained from acid leaching filtration of a metal-containing stream. This MMS production process can recover Ni and Co without incorporating lithium by taking advantage of the relative differences in solubility and concentration of the ions in the post-leaching solution. In one or more embodiments, if the unpurified MMS is not a suitable feed for pCAM without further purification, the method can include further purifying the MMS. For example, the method can purify MMS by oxidation and precipitation at high pH using a base such as caustic and a sulfide such as sodium sulfide. This treatment can remove impurities, such as Al, Cu, and Fe. Alternatively, the method can remove impurities from MMS using ion exchange (IX) or solvent extraction (SX). The method can provide the purified MMS for precursor cathode active material (pCAM) processing without further purification. Additionally, different metals can be mixed with MMS to adjust the metal ratio to suit the desired pCAM product. Additionally, the method can include purifying MMS outside of the overall recycling process by removing unpurified MMS in a separate process for subsequent redissolution and purification.

[0016] As described above, one or more implementations of the method can separate lithium from other base metals in solution by precipitation with hydrated lime. In some embodiments, this precipitation separation can receive as input the centrate remaining after producing MMS. The method can precipitate a mixed hydroxide precipitate (MHP) incorporating metals (e.g., Ni, Co, and Al) by adding hydrated lime to the input and leaving the lithium in solution. In addition to the MHP, this process produces gypsum. In one or more embodiments, the method includes removing the MHP and gypsum from the lithium-containing solution. The MHP and gypsum can then be sold as a combined product, or the gypsum and MHP can be separated for sale as separate products, or the MHP can be recycled to leaching. Production of MMS requires more processing but can result in a more purified product.

[0017] Additionally, in some implementations, the method can include recovering lithium by evaporating the lithium sulfate solution to produce Li2SO4 and converting the Li2SO4 to battery-grade LiOH. The method can include evaporating the lithium sulfate solution produced from precipitating the base metals with hydrated lime to isolate or recover Li2SO4. The method can include evaporating the lithium sulfate solution produced from precipitating the base metals with hydrated lime to isolate or recover Li2SO4 (whether in liquid or solid form, for example, Li2SO4 * HCl) to battery-grade LiOH or LiCO by electrolysis and / or conventional lithium conversion techniques. Additionally, the method can include recycling HSO produced as a by-product of the electrolysis of LiSO to the acid leaching of the mechanically separated battery material.

[0018] The present method offers various technical advantages over conventional systems. For example, by avoiding continuous solvent extraction and the formation of sodium sulfate by-product, the present method minimizes capital and operating costs and reduces environmental impact compared to conventional systems. Specifically, the disclosed method can avoid the formation of sodium sulfate by-product by separating base metals from lithium by precipitation with hydrated lime to produce MHP and by purifying MMS separately from the overall recycling process. In contrast, some conventional methods basify metals from lithium by continuous solvent extraction and / or separate Ni from Co as discrete salts using solvent extraction. Alternatively, conventional methods can separate base metals from lithium using recovery techniques such as precipitation with sodium-based reagents (e.g., sodium carbonate, sodium hydroxide). Such techniques result in the formation of sodium sulfate by-product, which can be costly to manage. For example, sodium sulfate must be separated from lithium, and then sodium sulfate and lithium must be recovered in separate stages. Furthermore, the use of sodium-based reagents also has a significant carbon dioxide footprint. One or more implementations avoid the costs associated with the above-described conventional methods by forming MMS as described herein.

[0019] Furthermore, by producing useful by-products and less problematic waste streams that can be recycled back into the process, the method further minimizes capital costs, generates new revenue, and reduces environmental impact. For example, the method can include recycling a Li-containing stream, such as a wash solution from filtering a metal-containing stream, to a hydrometallurgical circuit to reuse the solution and recover additional lithium. Furthermore, the method produces useful by-products, such as MHP and gypsum, which can be sold as combined products or used in the process of filtering a metal-containing solution to produce a hydrogen-metal concentrate. In one or more embodiments, by using these by-products in the filtration process, the method can eliminate the need for the use of filter aids, such as DE, thereby reducing costs and minimizing inputs. Additionally, the method can utilize HSO produced from converting LiSO via electrolysis as recycled input to the reductive acid leaching of mechanically separated battery manufacturing scrap material, thereby further minimizing process inputs.

[0020] Additionally, by minimizing inputs and accepting waste streams from the battery manufacturing process, the present method can further minimize costs and minimize environmental impact. For example, in some implementations, the present method can avoid the use of peroxides, resulting in significant reductions in operating costs. Also, using calcium-based products to separate lithium from base metals minimizes costs (e.g., because calcium-based products such as hydrated lime and calcium carbonate are low-cost reagents) and minimizes environmental impact as opposed to using sodium-based reagents as in conventional systems. Furthermore, the present method can incorporate the acid stream from the electrolytic treatment of sodium sulfate resulting from pCAM production during battery manufacturing into the recycling process. Doing so offsets a large portion of the sulfuric acid (H2SO4) input, thereby significantly improving economics, reducing the carbon footprint of the recycling process, and regenerating caustic for the pCAM process.

[0021] As described above, one or more implementations recover one or more different forms of Ni-containing products and lithium from battery manufacturing scrap materials. Further details of such methods are described below with reference to the drawings. Specifically, FIG. 1 illustrates an exemplary general process flow for recovering Ni-containing products and lithium. FIG. 2 illustrates an exemplary process flow for recovering lithium and Ni-containing products in the form of a hydrogen metal concentrate. FIG. 3 illustrates an exemplary process flow for recovering lithium, Ni-containing products in the form of a high nickel concentrate, and a composite product of MHP and gypsum. FIG. 4 illustrates an exemplary process flow for recovering lithium and Ni-containing products in the form of MMS.

[0022] FIG. 1 illustrates a process 100 for recovering Ni-containing products and lithium from battery manufacturing scrap material 102, according to one or more embodiments. Specifically, the process 100 can include processing the manufacturing material 102 through mechanical separation 104 to result in a black mass (BM) fraction 108. For example, in one or more implementations, the battery manufacturing scrap material includes manufacturing scrap (e.g., non-live production scrap or live production scrap). In either case, the process 100 begins with processing the manufacturing material 102 through mechanical separation 104. The mechanical separation 104 can utilize size sorting, size reduction, or screening to separate the various scrap materials. For example, the mechanical separation 104 can separate metals 122, such as cathode active materials (e.g., Al, Fe, Cu), from aluminum foil held together with a binder. Additionally, the mechanical separation 104 can separate graphite from copper foil, among other materials. Additionally, the method can optionally include reincorporating the separated aluminum foil and copper foil into a battery recycling process. Additionally, mechanical separation 104 can separate the separator material, which can be incorporated into the battery manufacturing process (e.g., polyolefin, ceramic, polymer / ceramic blend). Alternatively, the separator material may be sold to a third party. In one or more embodiments, the mechanical separation 104 process can result in a lithium- and various metal-containing black mass (BM) fraction 108, which is then utilized in additional processing steps in a hydrometallurgical circuit.

[0023] Further, in one or more implementations, the process 100 includes leaching 110 the BM 108 in a hydrometallurgical circuit. For example, the process 100 includes acid leaching 110 of the resulting BM 108. Indeed, the method may include adjusting the acid leaching 110 within an oxidation-reduction potential (ORP) range to optimize the selectivity and / or extraction rate of the process for specific metals. For example, the method may utilize a reductive acid leach including an acid 112 (e.g., sulfuric acid (H2SO4)), a peroxide 116, and water 114. In other embodiments, the method may utilize an oxidative acid leach including an acid 112 (e.g., sulfuric acid (H2SO4)) and water 114, but not a peroxide 116. In some embodiments, the acid leach may utilize other chemical compositions containing metals in different oxidation states than other recycling processes, such as when black mass is generated by thermal treatment.

[0024] In one or more embodiments, the acid leaching 110 liberates substantially all of the metals into solution, leaving behind graphite material. For example, the metal-containing stream can include Ni, Co, Al, Li, and Cu as sulfates (i.e., a metal sulfate solution) and graphite. In some embodiments, the acid leaching 110 can liberate substantially all of the lithium into solution. For example, the acid leaching 110 can liberate greater than 95%, 90%, 85%, 80%, 75%, 70%, 65%, 55%, or greater than 50% of the lithium into solution. Furthermore, in one or more implementations, the acid leaching 110 can liberate 30-50%, 20-60%, or 10-98% of the Ni, Co, and Al. In some embodiments, process 100 can further include filtering the metal-containing stream resulting from acid leaching 110 for subsequent processes, such as process 117 to recover Ni-containing products and process to recover LiSO via evaporation and electrolysis or other conventional lithium conversion techniques.

[0025] Additionally, in some implementations, the process 100 includes a process 117 for recovering a Ni-containing product 118 from the metal-containing stream resulting from the acid leaching 110. For example, the process 100 may recover the Ni-containing product 118 in the form of a hydrogen metal concentrate, as described in more detail in connection with FIG. 2, a high-nickel concentrate and MHP / gypsum product, as described in more detail in connection with FIG. 3, or MMS and MHP / gypsum, as described in more detail in connection with FIG. 4. Indeed, the process 100 may include recovering the Ni-containing product 118 using various methods, such as precipitating metals from the stream resulting from the acid leaching 110, filtering the stream, and / or producing MMS using an evaporator and / or crystallizer, as discussed in more detail in connection with FIGS. 2-4. In any event, the process 117 for recovering a Ni-containing product from the stream resulting from the acid leaching produces one or more Ni-containing products 118 and a lithium sulfate solution 119.

[0026] As described above, in one or more implementations, the method can include recovering lithium from the lithium sulfate solution 119. For example, in one or more implementations, the method can include processing the lithium sulfate solution in a lithium sulfate evaporator 120 to produce LiSO 124 and water 122, which the method can recycle back to the battery recycling process. The method can further retain the LiSO 124 as a solution or solid (e.g., lithium sulfate monohydrate (LSM)) for later redissolution.

[0027] In one or more embodiments, process 100 can further include converting LiSO 124 via lithium electrolysis process 126. In one or more embodiments, process 100 can include converting LiSO 124 to LiCO (indirectly) or to battery-grade LiOH 128 (directly) via electrolysis. Electrolysis can also produce dilute acid (e.g., dilute HSO 130) as a by-product. In one or more embodiments, process 100 can include recycling the HSO 130, a by-product of lithium electrolysis process 126, to acid leach 110, as described above. Additionally, process 100 can include maintaining a water balance such that process 100 can return the HSO 130 to a battery recycling process (e.g., back to acid leach 110) or to another manufacturing process. In one or more additional embodiments, other conventional lithium recovery processes are used.

[0028] As described above, one or more embodiments include recovering a nickel-containing product in the form of a hydrogen metal concentrate and lithium from battery manufacturing scrap materials. For example, FIG. 2 illustrates a process 200 for recovering lithium and a hydrogen metal concentrate 222 from a metal-containing stream resulting from acid leaching 210, according to one or more embodiments. Specifically, process 200 can include processing manufacturing material 202 through mechanical separation 204 to produce a BM fraction 208 (or BM 208), similar to mechanical separation 104 of process 100. Indeed, mechanical separation 204 can separate similar metals 206 (e.g., Al, Fe, Cu) and various other battery materials in a manner similar to, and for similar purposes as, those described above with respect to mechanical separation 104. Also, in one or more embodiments, mechanical separation 204 results in a BM 208 of a similar composition to BM 108, as described.

[0029] Further, in one or more implementations, the process 200 includes acid leaching 210 the BM 208. For example, the method utilizes acid 212 and water 214 for the acid leaching 210. In one or more embodiments, the method excludes peroxide from the acid leaching 210 to tailor the process to be selective for lithium. In these or other embodiments, the method targets lithium in the BM 208 by tailoring the conditions of the acid leaching 210 to be within the oxidizing portion of the ORP. When leaching without peroxide, the acid leaching 210 can operate at an ORP of about 800 to about 1200 and a pH of about 1.0 to about 4.0. In some implementations, the method also utilizes recycled H2SO4 242 in the acid leaching 210, as described in more detail below. Furthermore, in some embodiments, the method can utilize recycled wash solution 224 resulting from a subsequent filtration process, as discussed in more detail below.

[0030] In one or more implementations, acid leaching 210 is performed using sulfuric acid 212 and water 214, which liberates nearly all of the lithium into solution, but only about 30-50% of the Ni, Co, and Al. In effect, acid leaching 210 produces a solution containing metals (e.g., Ni, Co, Al, Li, and Cu as sulfates).

[0031] Further, in one or more embodiments, the process 200 includes treating the metal-containing slurry resulting from the acid leaching 210 to recover a hydrogen metal concentrate 222 (e.g., a composite product containing a high nickel concentrate, a mixed hydroxide precipitate (MHP), and gypsum). Specifically, in one or more embodiments, the metal precipitation process 216 is carried out using lime 218. Specifically, the method can include separating base metals in the metal-containing stream from lithium by adding slaked lime 218 (i.e., Ca(OH)2) to precipitate the base metals from the solution. In these or other embodiments, the slaked lime 218 raises the pH to produce MHP and gypsum. The high pH allows for the formation of MHP without incorporating lithium. In some embodiments, the method can include using limestone (CaCO3) to bring the solution to a pH of about 6.0, and then treating 218 the feed solution with slaked lime. Furthermore, the addition of hydrated lime 218 typically forms gypsum that contaminates the resulting base metal precipitate (e.g., MHP).

[0032] In this implementation, method 200 further includes a metal slurry filtering process 220. Notably, metal slurry filtering process 220 does not require a filter aid, in contrast to other methods described below with respect to FIG. 3 . Indeed, filtering the metal slurry recovers a hydrogen metal concentrate 222, a valuable composite product containing a high nickel concentrate, MHP, and gypsum. Furthermore, hydrogen metal concentrate 222 is suitable and acceptable for transportation (e.g., bulk transportation) even without a filter aid. Furthermore, in some implementations, metal slurry filtering process 220 utilizes a wash solution 224 that can replace a portion of the lithium in the solution phase. In these or other embodiments, the method includes recycling wash solution 224 to acid leach 210 to recover lithium. By incorporating metal precipitation process 216 and metal slurry filtering process 220, process 200 achieves separation of base metals from lithium in solution while avoiding various drawbacks of conventional methods, such as those described above.

[0033] Additionally, as shown, the process 200 includes calcium precipitation 226 of the lithium-containing solution remaining after recovery of the hydrogen metal concentrate 222. Specifically, in some embodiments, the calcium precipitation 226 includes the use of soda ash or carbon dioxide (CO2) 228. Additionally, the calcium precipitation 226 can include continuously withdrawing the soda ash and / or carbon dioxide to reduce the calcium concentration in the lithium-containing solution.

[0034] The addition of soda ash or carbon dioxide can minimize or prevent the formation of soluble calcium from being carried over to the lithium evaporator for subsequent processing. By minimizing or preventing the passage of soluble calcium to subsequent processes, the method achieves benefits such as preventing fouling and contamination in subsequent processes and preventing adverse effects on product quality.

[0035] Calcium precipitation can result in lithium sulfate solution 232 and calcium carbonate (CaCO) 230 by-products. The calcium precipitation step can also result in CaCO 3. In one or more embodiments, the method recycles the CaCO3 230 to the metal precipitation process 216. The lithium sulfate solution 232 can be further processed to recover lithium-containing products such as Li2CO3 and LiOH.

[0036] As described above, in one or more implementations, the process 200 includes recovering lithium from the lithium sulfate solution 232. For example, the method can include a process 234 for evaporating the lithium sulfate solution to produce LiSO and a process 240 for converting the LiSO to LiCO and LiOH via a lithium electrolysis process (also referred to simply as electrolysis). In one or more embodiments, the process 234 for evaporating the lithium sulfate solution produces water 236 and LiSO. In these or other embodiments, the method can recycle the water 236 back to the battery recycling process while retaining the LiSO as a solution or solid crystals for later redissolution. In some implementations, the process 240 for converting the lithium sulfate can include converting the LiSO to battery-grade LiOH using a combination of electrolysis and precipitation. Additionally, in some implementations, the lithium sulfate conversion process 240 utilizes CO precipitation of LiOH 246 to produce LiCO 244. This recovery and conversion avoids the formation of sodium sulfate, which is typical of conventional systems and has the challenges discussed herein.

[0037] As mentioned above, in some implementations, process 200 further includes recycling HSO 242, a by-product of lithium sulfate converting process 240, to acid leach 210. In one or more embodiments, the recycling of HSO 242 is similar to the recycling of HSO 130 described above with respect to lithium electrolysis process 126. For example, lithium sulfate converting process 240 produces dilute HSO 242 as a by-product, which the method can recycle to acid leach 210 to offset acid 212 input or use in other manufacturing processes. Furthermore, in one or more implementations, process 200 includes maintaining a water balance in the hydrometallurgical circuit to enable this recycling of dilute HSO 242.

[0038] As described above, one or more embodiments include recovering a high nickel concentrate and a nickel-containing product in the form of lithium from battery manufacturing scrap materials. For example, FIG. 3 illustrates a process 300 for recovering a high nickel concentrate 320 from a metal-containing stream resulting from acid leaching 310, according to one or more embodiments. Specifically, process 300 may include processing manufacturing material 302 via mechanical separation 304 to produce a BM fraction 308 (or BM 308). In one or more embodiments, mechanical separation 304 is similar to mechanical separation 104 described above. Indeed, mechanical separation 304 may separate similar metals 306 (e.g., Al, Fe, Cu) and various other battery materials in a manner similar to, and for similar purposes as, described above with respect to mechanical separation 104. Also, in one or more embodiments, mechanical separation 304 results in BM 308 of a similar composition to BM 108, as described above.

[0039] Further, in one or more embodiments, the process 300 includes acid leaching 310 of the BM 308. In some implementations, the acid leaching 310 can be substantially similar in process and components to those described above with respect to the acid leaching 210. For example, the acid leaching 310 can include incorporating acid 312 and water 314, as well as a wash solution 332, as described in more detail with respect to the MHP filtration / separation 326. Furthermore, the acid leaching 310 produces a metal-containing stream similar to that described above with respect to the acid leaching 210. Specifically, as shown, the acid leaching 310 process can be tailored to liberate lithium into solution. For example, when leaching without peroxide, the acid leaching 210 can operate at an ORP of 800-1200 and a pH of 1.0-4.0.

[0040] As mentioned above, in some implementations, the process 300 includes treating the metal-containing stream resulting from the acid leaching 310 to recover a high nickel concentrate 320. Specifically, in one or more embodiments, treating the metal-containing stream resulting from the acid leaching 310 may include a metal stream filtering process 316, a metal precipitation process 322, and an MHP filtration / separation process 326.

[0041] As described above, the method can include filtering the metal-containing stream after acid leaching 310, as shown in FIG. 3 . Specifically, in some embodiments, the process 316 for filtering the metal stream utilizes a filter aid 318 to produce a high-nickel concentrate 320. For example, the method can include utilizing a filter aid 318 when sending the metal stream produced from acid leaching 310 to a filter tank, as shown in FIG. 3 . Filtering the metal stream using the filter aid 318 results in a clear filtrate and a filter cake suitable for transportation. In some implementations, the filter aid 318 can include a commonly used filter aid, such as diatomaceous earth (DE). Furthermore, in some embodiments, the filter aid 318 can be used at a dilution of 5-25% to provide a clear filtrate and for optimal filtration performance (e.g., filtration rate, solution purity, and wash efficiency). In one or more implementations, the dilution of the filter aid 318 can be 2-35% or 1-50%. Alternatively, in some embodiments, filtering the metal stream can include the use of chemical additives, such as filter flocculants, in place of the filter aid 318 .

[0042] As mentioned above, in some implementations, processing the metal-containing stream resulting from acid leaching 310 further includes precipitating metals from a filtered metal solution. For example, in these or other embodiments, the filtered metal solution remains after recovering the high-nickel concentrate 320. This filtered metal solution contains base and other metals (e.g., Co and Al), which method 300 separates from lithium by a metal precipitation process 322 using lime 324 (e.g., hydrated lime). This metal precipitation process 322 is substantially similar to the metal precipitation process 216 described above, except that metal solution filtering process 316 recovers most of the Ni from the solution prior to metal precipitation process 322. Indeed, in these or other embodiments, metal precipitation process 322 using hydrated lime 324 forms MHP 328 and gypsum 330 without incorporating lithium. Thus, metal precipitation process 322 results in a lithium-containing solution.

[0043] Additionally, in some implementations, metal precipitation process 322 can incorporate calcium carbonate (CaC0) 338 from calcium precipitation 334, described in more detail below. For example, CaC0 3338 can act as a neutralizing agent in metal precipitation process 322 by reacting with a portion of the acid to raise the pH. In these or other embodiments, by incorporating recycled CaC0 3338, the method recycles what would otherwise be a waste stream.

[0044] As mentioned above, in some embodiments, the treatment of the metal-containing solution resulting from the acid leach 310 also includes MHP filtration / separation 326. For example, the method may include MHP filtration / separation 326 of the lithium-containing solution resulting from the metal precipitation process 322. In some implementations, the MHP filtration / separation 326 filters MHP 328 and gypsum 330 from the lithium-containing solution. However, as shown, in one or more embodiments, the MHP filtration / separation 326 separates the gypsum 330 from the MHP 328. Indeed, the method includes separating the gypsum 330 from the MHP 328 by taking advantage of the size difference between the metal precipitate and the gypsum 330. Furthermore, in some implementations, the MHP filtration / separation 326 utilizes a wash solution 332 that can replace a portion of the lithium in the solution phase. In these or other embodiments, the method may include recycling the wash solution 332 to the acid leach 310 to recover lithium and reuse what would otherwise be a waste stream.

[0045] As mentioned above, in one or more embodiments, MHP filtration / separation 326 separates gypsum from MHP 328 by taking advantage of size differences. In these or other embodiments, the method includes growing gypsum crystals to an appropriate size to enable separation of gypsum 330 and base metals by controlling process conditions (e.g., temperature, time, etc.) and recycling a portion of gypsum 330 in the process. In some embodiments, some of the base metals may become entrained in the gypsum phase. In these or other embodiments, the method may include removing these metals through an acid wash process performed using solid / liquid separation techniques (e.g., centrifugation). In other embodiments, the method may include directing MHP 328 to other battery recycling processes, or MHP 328 may be sold separately.

[0046] As described above, in one or more embodiments, process 300 includes calcium precipitation 334 of the lithium-containing solution, resulting in lithium sulfate solution 340. In some implementations, calcium precipitation 334 is substantially similar to calcium precipitation 226 described above and offers similar advantages. For example, calcium precipitation 334 can include providing CO or soda ash 336 to the lithium-containing solution, resulting in a CaCO by-product 338, which can be recycled to process 322 for precipitating the metal. Also, like calcium precipitation 226, calcium precipitation 334 results in lithium sulfate solution 340. In one or more embodiments, CO does not result in Na in the final product, which helps prevent lithium loss due to controlling the level of sodium in the final product.

[0047] As mentioned above, in some implementations, process 300 includes recovering lithium from lithium sulfate solution 340 by process 348, which converts LiSO to LiCO and / or LiOH. For example, in one or more embodiments, process 348, which converts LiSO to LiCO and / or LiOH, is substantially similar to process 240, which converts LiSO, described above, and therefore will not be discussed further. Furthermore, in some embodiments, LiSO is also produced from process 342, which evaporates the lithium sulfate solution, and is substantially similar to process 234, which evaporates the lithium sulfate solution, discussed above. Indeed, process 342, which evaporates the lithium sulfate solution, also produces water 344, which the method may include recycling back to the battery recycling process.

[0048] As mentioned above, in one or more embodiments, the process 300 includes recycling H2SO4 350, a by-product of the lithium sulfate converting process 348, to the acid leach 310. For example, recycling of H2SO4 242 can be similar to the recycling of H2SO4 242 described above and therefore will not be discussed further.

[0049] As described above, one or more embodiments involve recovering nickel-containing products in the form of MMS and lithium from battery manufacturing scrap materials. For example, FIG. 4 illustrates a process 400 for recovering MMS from a metal-containing stream resulting from acid leaching 410, according to one or more embodiments. Specifically, process 400 can include processing manufacturing material 402 via mechanical separation 404 to produce a BM fraction 408 (or BM 408). Generally, process 400 involves processing manufacturing material 402 from the production of lithium-ion batteries to a product that the method can then feed back into the battery materials supply chain. In some implementations, implementation of process 400 minimizes capital and operating costs while lowering environmental impact by avoiding the formation of sodium sulfate by-product.

[0050] As described above, in some implementations, the process 400 includes processing the manufacturing material 402 through mechanical separation 404 to produce a BM 408. The mechanical separation 402 can utilize size sorting, size reduction, or screening to separate various scrap materials. For example, the mechanical separation 402 can separate metals 406 (e.g., Al, Fe, Cu). As an example, the mechanical separation 402 can separate cathode active material from aluminum foil held with a binder. Furthermore, the mechanical separation 404 can separate graphite from copper foil, among other materials. Furthermore, the method can optionally include reincorporating the separated aluminum foil and copper foil into other battery recycling processes. Furthermore, the mechanical separation can separate separator material, which (e.g., polyolefin, ceramic, polymer / ceramic blend) can be incorporated into other battery manufacturing processes. Alternatively, the separator material may be sold to a third party. In one or more embodiments, the mechanical separation 402 process can result in a lithium- and various metal-containing black mass (BM) fraction 408, which can be utilized in additional processing steps. Indeed, mechanical separation 404 can separate metals 406 (e.g., Al, Fe, Cu) and various other battery materials in a manner and for similar purposes as described above with respect to mechanical separation 104. Also, in one or more embodiments, mechanical separation 404 results in BM 408 of similar composition to BM 108, as described.

[0051] Further, in one or more implementations, the process 400 includes acid leaching 410 the BM 408 in a hydrometallurgical circuit. In particular, the acid leaching 410 process includes a reductive acid leaching process utilizing acid 414 (e.g., sulfuric acid (H2SO4)), peroxide 412, and water 416. In these or other embodiments, the method includes adjusting the conditions of the acid leaching 410 to be within the reducing portion of the ORP. Specifically, the acid leaching 410 can operate at an ORP of about 500 to about 800 and a pH of about 1.0 to about 4.0. In some implementations, the method also utilizes recycled H2SO4 458 in the acid leaching 410, as described in further detail below.

[0052] In one embodiment, the acid leaching 410 liberates substantially all of the metals into a metal solution. For example, the metal solution can include Ni, Co, Al, Li, and Cu as sulfates (e.g., a metal sulfate solution) and graphite. In some embodiments, the acid leaching 410 can liberate substantially all of the lithium into solution. For example, the acid leaching can liberate greater than 90%, greater than 80%, greater than 70%, greater than 60%, or greater than 50% of the lithium into solution. Furthermore, in one or more implementations, the acid leaching 410 can liberate 30-50%, 20-60%, or 10-98%. As shown, the process 400 further includes an acid leaching filtration 418 step that separates the graphite 420.

[0053] As described above, process 400 includes treating the metal-containing stream resulting from acid leaching 410 and filtration 418 to recover MMS. For example, the method includes producing MMS 422. Specifically, the process for producing MMS 422 includes producing MMS of nickel and cobalt sulfate from the metal-containing filtrate using an evaporator and / or crystallizer. In these and other embodiments, the method can recover approximately 80% of the Ni and Co, with negligible recovered lithium. In some embodiments, the process for producing MMS 422 can recover more or less of the Ni and Co, with negligible recovered lithium. For example, the process for producing MMS 422 can recover 75-85%, 70-90%, 60-95%, or 50-99% of the Ni and Co. In one or more implementations, the resulting mother liquor can contain substantially all of the lithium and approximately 20% of the unrecovered Ni and Co. In some implementations, the resulting mother liquor can be depleted in lithium and enriched in Ni and Co. For example, in these or other embodiments, the resulting mother liquor can contain 90-95% lithium, 80-90% lithium, 70-80% lithium, or 60-70% lithium. Further, in these or other embodiments, the resulting mother liquor can contain 15-25%, 10-30%, 5-40%, or 1-50% Ni and Co.

[0054] Specifically, in one or more embodiments, the process 422 for producing MMS includes evaporating and / or crystallizing Ni and Co from a Mn / Ni / Co / Li solution stream (e.g., a metal-containing filtrate). In one or more implementations, the process for producing MMS 422 may also include controlling the degree of evaporation and / or crystallization so that lithium is not included in the MMS, leaving the lithium in the residual solution (i.e., centrate) coming from the centrifuge. The centrifuge separates the MMS solid crystals from the solution phase (e.g., centrate). In one or more embodiments, the MMS contains about 70-80% Ni / Co, and the centrate contains all of the residual Ni / Co and lithium. In other embodiments, the MMS can contain about 60-90% or about 50-95% Ni / Co, and the centrate contains the residual Ni / Co, in each case. Additionally, in some implementations, the residue may contain less lithium, for example, about 90-99%, about 80-95%, or about 70-90% lithium. In one or more embodiments, the MMS at this stage is not conventional battery grade, but can be sold as crude MMS, with major impurities including Al, Cu, and Fe, among others.

[0055] As mentioned above, in some implementations, the method includes process 424 of purifying MMS and recycling purified MMS 426 to pCAM process 428. Optionally, in some embodiments, rather than integrating MMS impurity removal in process 400 (which can result in significant capital expenditure complications), the process includes shifting MMS purification to an external circuit more suitable for pCAM integration. Specifically, the use of sodium reagents and the presence of lithium in MMS purification and pCAM can result in complications in the separation of sodium and lithium. In these or other embodiments, after redissolving MMS in solution in a separate process, the method can include providing dissolved and purified MMS 426 as a solution to pCAM process 428. In one or more embodiments, process 424 of purifying MMS includes oxidation and precipitation at high pH levels and the use of sulfides (e.g., sodium sulfide), caustic, and / or peroxides.

[0056] In one or more embodiments, the method can include incorporating other purification techniques for process 424 to purify MMS, as would be understood by one of ordinary skill in the art. For example, process 424 to purify the MMS solution can include any one of a variety of methods, such as oxidation and precipitation at high pH, ​​ion exchange or solvent extraction, or other purification techniques. Process 424 to purify MMS can purify MMS to have contaminant impurity levels of less than about 10 ppm, or less than about 7 ppm, or less than about 6 ppm, or less than about 5 ppm, or less than about 4 ppm, or less than about 3 ppm, or less than about 2 ppm, or less than about 1 ppm.

[0057] As mentioned above, in some implementations, after purifying the MMS solution to produce MMS that is a suitable feedstock for pCAM without further purification, the method can further utilize the purified MMS 426 in pCAM processing 428. For example, process 428 can include mixing the MMS solution with other metal sources to adjust the metal ratio to suit the desired pCAM product, and also act as a diluent for impurities.

[0058] As mentioned above, in some implementations, process 400 includes process 430 for precipitating harmful elements, such as, but not limited to, Fe, Al, and Cu, from the centrate remaining after recovering MMS. More specifically, the method can include separating the metals in the concentrate from lithium. For example, process 430 for precipitating the metals can include adding lime 432 (e.g., Ca(OH)2) to the centrate to raise the pH to a level of about 2.0 to about 5.0. In these embodiments, the high pH causes the formation of MHP 436 and gypsum 434. Furthermore, this MHP 436 contains some metals (e.g., Ni and Co) in solution, but no lithium. In one or more embodiments, process 422 for producing MMS can only evaporate most of the MMS solution before initiating lithium incorporation. Thus, in some implementations, producing MMS includes ending evaporation before incorporating lithium. Thus, in these or other embodiments, the centrate contains all of the lithium.

[0059] Further, in one or more embodiments, step 430 of precipitating metals optionally includes using limestone (CaCO) to bring the solution to a pH of about 6.0 and then treating the feed solution with hydrated lime in step 432. Furthermore, in some embodiments, gypsum 434 contaminates the resulting MHP 436, rendering it low-grade. However, in these embodiments, the method may include separating gypsum 434 from the base metal precipitate by taking advantage of the size difference between the metal precipitate and gypsum 434. For example, in these or other embodiments, the method may include growing gypsum crystals to an appropriate size to enable separation of gypsum 434 and the metal by controlling process conditions (e.g., temperature, time, etc.) and recycling a portion of gypsum 434 in the process. In some embodiments, some of the base metals may become entrained in the gypsum phase. In these or other embodiments, the method may include removing these metals through an acid wash process performed using solid / liquid separation techniques (e.g., centrifugation). In other embodiments, the method can include directing MHP 436 to other battery recycling processes, or MHP 436 can be sold separately. Thus, metal precipitation process 430 is low cost, simple, and allows for the recovery of various base metals. It also does not precipitate lithium, making it transferable to subsequent lithium recovery processing.

[0060] In one or more embodiments, metal precipitation process 430 can also precipitate MHP 436 in a manner that first removes Al, allowing for the recycling of the resulting Ni and Co to reductive acid leach 410 and the incorporation of Ni and Co units into MMS. This can introduce calcium into the MMS circuit, but this can be managed by controlling the configuration of the MMS evaporator and then removing the calcium in process 424 to purify MMS using IX or SX. In another embodiment, the method can include using MHP 436 as a precipitant for Al and Fe prior to the MMS evaporator. In this or other embodiments, the method can include controlling the removal of calcium in the MMS evaporator and / or in the MMS purification circuit.

[0061] As previously mentioned, in one or more embodiments, process 400 includes calcium precipitation 438 of the lithium-containing solution resulting from metal precipitation process 430. For example, calcium precipitation 438 can include continuously withdrawing soda ash and / or carbon dioxide 440 to reduce the calcium concentration in the solution. As described above with respect to calcium precipitation 226, this prevents fouling and contamination in subsequent processes and adverse effects on product quality. In some embodiments, calcium precipitation 438 provides CaC03 442. In these or other embodiments, the method includes recycling CaC03 442 to metal precipitation process 430, which provides benefits similar to those described above with respect to CaC03 230 in FIG. 2. In some embodiments, in addition to providing lime, metal precipitation process 430 can include simultaneously providing soda ash and / or carbon dioxide 440 to reduce the calcium concentration. In these or other embodiments, the method includes providing soda ash or carbon dioxide after precipitating MHP 436 to avoid contact of the soda ash or carbon dioxide with lime 432 or gypsum 434.

[0062] The above-described embodiment of the process 430 for precipitating metals from the centrate avoids the formation of sodium sulfate, which is traditionally used in MHP 436 precipitation or impurity removal and must be treated as part of the recycling process. This can be particularly problematic in traditional processes because, if lithium is also present, the lithium and sodium must be separated, which leads to additional time, cost, and complexity. For example, traditional systems form sodium sulfate and must separate the sodium sulfate from LiSO.

[0063] As mentioned above, in some embodiments, the method can include recovering lithium as a lithium sulfate salt by converting LiSO to battery-grade LiOH and / or LiCO. Similar to the lithium recovery and conversion described above with respect to Figure 2, this recovery and conversion also avoids the formation of sodium sulfate, which has the challenges discussed above.

[0064] In one or more embodiments, the metal precipitation process 430 and calcium precipitation 438 result in a lithium sulfate solution 444. In some embodiments, the process 400 includes a process of evaporating the lithium sulfate solution 444, which results in water 448, which the method can recycle back to the battery recycling process. The method can retain the Li2SO4 450 as a solution or solid crystals for later redissolution. The process 400 can further include converting the Li2SO4 450 by electrolysis.

[0065] As mentioned above, in one or more embodiments, process 400 includes process 452, which converts lithium sulfate to LiCO 454 (indirectly) or battery-grade LiOH 456 (directly) via electrolysis. Indeed, in some embodiments, process 452 can be substantially similar to process 240, which converts lithium sulfate, described above. Additionally, electrolysis can also produce dilute acid (e.g., dilute HSO 458) as a by-product. Furthermore, process 400 can include maintaining a water balance, such that process 400 can include recycling the HSO 458 back into the battery recycling process (e.g., back into reductive acid leach 410) or for use in other manufacturing processes. As a result, the system can offset a portion of the acid 414 input into acid leach 410, significantly improving the economics and carbon footprint of the recycling process, while also regenerating caustic for the pCAM process.

[0066] 1-4, the corresponding text, and examples provide several different systems and methods for recovering lithium- and nickel-containing products from battery manufacturing scrap materials with improved by-products and minimal waste streams. In addition to the above, embodiments may also be described in terms of flowcharts that include operations for achieving particular results. For example, FIGS. 5-7 illustrate flowcharts of exemplary sequences of operations according to one or more embodiments. While FIGS. 5-7 illustrate operations according to some embodiments, alternative embodiments may omit, add, reorder, and / or modify any of the operations illustrated in FIGS. 5-7. Furthermore, operations described herein may be repeated or performed in parallel with each other or with different instances of the same or other similar operations.

[0067] FIG. 5 illustrates an exemplary sequence of operations 500 for recovering lithium and nickel-containing products from battery manufacturing scrap material. The sequence of operations 500 can include operation 502, leaching the battery manufacturing scrap material in an acidic solution to produce a metal (e.g., Ni, Co, and Li)-containing stream. The sequence of operations 500 can include operation 504, treating the stream to recover one or more nickel-containing products and to produce a lithium sulfate solution. For example, operation 504 can include treating the stream to recover one or more nickel-containing products by treating the metal-containing stream to recover mixed metal sulfates (MMS) and producing a lithium-containing centrate. Further, in one or more embodiments, operation 504 can include purifying the MMS by oxidation and precipitation at a high pH level of 2.0 to 5.0. Further, operation 504 can include providing the purified MMS as a feed to a precursor cathode active material (pCAM) process. Further, operation 504 can include utilizing a calcium-based product to precipitate one or more metals from the lithium-containing centrate without producing sodium-containing by-products.

[0068] Further, in one or more implementations, operation 504 can include treating the stream to recover one or more nickel-containing products by treating the stream to recover a hydrogen metal concentrate comprising mixed hydroxide precipitate (MHP), gypsum, and a high nickel concentrate. Further, in one or more embodiments, treating the stream to recover a hydrogen metal concentrate includes utilizing a calcium-based product to precipitate one or more metals from the stream to produce the MHP, gypsum, and a lithium-containing solution. Further, in some embodiments, operation 504 can further include treating the stream to recover a hydrogen metal concentrate by filtering the MHP, gypsum, and high nickel concentrate from the lithium-containing solution.

[0069] Further, in some implementations, operation 504 may include treating the stream to recover one or more nickel-containing products by treating the stream to recover a high nickel concentrate. Further, operation 504 may include treating the stream to recover a high nickel concentrate by filtering the high nickel concentrate from the stream using a filter aid. Further, operation 504 may further include precipitating one or more metals from the stream using a calcium-based product to produce a mixed hydroxide precipitate (MHP), gypsum, and a lithium-containing solution. Further, operation 504 may include removing the MHP and gypsum from the lithium-containing solution.

[0070] The series of operations 500 can include an operation 506 of evaporating the lithium sulfate solution to produce lithium sulfate (LiSO). In one or more implementations, operation 506 can further include converting the lithium sulfate (LiSO) to at least one of lithium hydroxide (LiOH) or lithium carbonate (LiCO) by electrolysis or other conventional lithium recovery methods.

[0071] 6 shows an exemplary sequence of operations for recovering lithium and hydrogen metal concentrate from battery manufacturing scrap material. Sequence 600 can include operation 602, leaching the battery manufacturing scrap material in an acidic solution to produce a metal (e.g., Ni, Co, and Li)-containing stream.

[0072] The series of operations 600 may include operation 604 of treating the stream to recover a hydrogen metal concentrate and produce a lithium sulfate solution without producing sodium-containing by-products. Furthermore, in some embodiments, operation 604 may further include utilizing lime to precipitate metals from the metal-containing solution to produce a mixed hydroxide precipitate (MHP), gypsum, and a lithium-containing solution. Additionally, in one or more implementations, operation 604 may further include recovering the hydrogen metal concentrate, including the high nickel concentrate, MHP, and gypsum, by filtering from the lithium-containing solution. Furthermore, operation 604 may further include precipitating calcium from the lithium-containing solution using at least one of soda ash or carbon dioxide. Furthermore, the series of operations 600 may include operation 606 of evaporating the lithium sulfate solution to produce lithium sulfate (LiSO).

[0073] 7 shows an exemplary sequence of operations 700 for recovering lithium and high nickel concentrates from battery manufacturing scrap material. The sequence of operations 700 can include an operation 702 of leaching the battery manufacturing scrap material in an acidic solution to produce a metal (e.g., Ni, Co, and Li)-containing stream.

[0074] Further, the series of operations 700 may include an operation 704 of treating the stream to recover a high nickel concentrate and produce a lithium sulfate solution without producing sodium-containing by-products. For example, operation 704 may include treating the stream to recover a high nickel concentrate by filtering the high nickel concentrate from the solution utilizing a diatomaceous earth filter aid. Further, the series of operations 700 may include adding lime to precipitate one or more metals from the stream to produce a mixed hydroxide precipitate (MHP), gypsum, and a lithium-containing solution.

[0075] In the foregoing specification, the invention has been described with reference to specific exemplary embodiments thereof. Various embodiments and aspects of the invention will be described with reference to the details discussed herein, and the accompanying drawings illustrate various embodiments. The above description and drawings are illustrative of the invention and should not be construed as limiting the invention. Numerous specific details are set forth in order to provide a thorough understanding of various embodiments of the invention.

[0076] The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects as illustrative only and not restrictive. For example, the methods described herein may be performed with fewer or more steps / actions, or the steps / actions may be performed in a different order. Moreover, the steps / actions described herein may be repeated or performed in parallel with each other or with different instances of the same or similar steps / actions. The scope of the present invention is, therefore, indicated by the appended claims, rather than by the foregoing description. All changes that come within the meaning and range of equivalency of the claims are to be embraced within their scope.

Claims

1. leaching battery manufacturing scrap material in an acidic solution to produce a stream comprising nickel (Ni), cobalt (Co), and lithium (Li); treating the stream to recover one or more nickel-containing products and produce a lithium sulfate solution; and The lithium sulfate solution was evaporated to obtain lithium sulfate (Li ２ SO ４ and generating a

2. 10. The method of claim 1, wherein treating the stream to recover one or more nickel-containing products comprises treating the stream to recover mixed metal sulfates (MMS) and producing a lithium-containing centrate.

3. 3. The method of claim 2, further comprising purifying the MMS by oxidation and precipitation of deleterious elements such as, but not limited to, Fe, Al, and Cu at a high pH level of 2.0 to 5.

0.

4. 4. The method of claim 3, further comprising providing the purified MMS as a feed to a precursor cathode active material (pCAM) process.

5. 3. The method of claim 2, further comprising utilizing a calcium-based product to precipitate one or more metals from the lithium-containing centrate without producing sodium-containing by-products.

6. 10. The method of claim 1, wherein treating the stream to recover one or more nickel-containing products comprises treating a slurry to recover a mixed hydroxide precipitate (MHP), gypsum, and a hydrogen metal concentrate comprising a high nickel concentrate.

7. 7. The method of claim 6, wherein treating the stream to recover the hydrogen metal concentrate comprises utilizing a calcium-based product to precipitate one or more metals from the stream to produce the MHP, the gypsum, and a lithium-containing solution.

8. 8. The method of claim 7, wherein treating the stream to recover the hydrogen metal concentrate further comprises filtering the MHP, the gypsum, and the high nickel concentrate from the lithium-containing solution.

9. The method of claim 1 , wherein treating the stream to recover one or more nickel-containing products comprises treating the stream to recover a high nickel concentrate.

10. 10. The method of claim 9, wherein treating the stream to recover the high nickel concentrate comprises filtering the high nickel concentrate from the stream utilizing a filter aid.

11. 11. The method of claim 10, further comprising utilizing a calcium-based product to precipitate one or more metals from the filtered stream to produce a mixed hydroxide precipitate (MHP), gypsum, and a lithium-containing solution.

12. 12. The method of claim 11 further comprising removing the MHP and the gypsum from the lithium-containing solution.

13. The lithium sulfate (Li ２ SO ４ ) is converted by electrolysis into lithium hydroxide (LiOH) or lithium carbonate (Li ２ CO ３ 10. The method of claim 1, further comprising converting the

14. leaching battery manufacturing scrap material in an acidic solution to produce a stream comprising nickel (Ni), cobalt (Co), and lithium (Li); treating said stream to recover a hydrogen metal concentrate and produce a lithium sulfate solution without producing sodium-containing by-products; and The lithium sulfate solution was evaporated to obtain lithium sulfate (Li ２ SO ４ and generating a

15. 15. The method of claim 14, further comprising utilizing lime to precipitate one or more metals from the stream to produce a mixed hydroxide precipitate (MHP), gypsum, and a lithium-containing solution.

16. 16. The method of claim 15, further comprising recovering the hydrogen metal concentrate comprising the high nickel concentrate, the MHP, and the gypsum from the lithium-containing solution by filtration.

17. 17. The method of claim 16, further comprising precipitating calcium from the lithium-containing solution with at least one of soda ash or carbon dioxide to produce the lithium sulfate solution.

18. leaching battery manufacturing scrap material in an acidic solution to produce a stream comprising nickel (Ni), cobalt (Co), and lithium (Li); treating the metal-containing stream to recover a high nickel concentrate by filtration and produce a lithium sulfate solution without producing sodium-containing by-products; and The lithium sulfate solution was evaporated to obtain lithium sulfate (Li ２ SO ４ and generating a

19. 20. The method of claim 18, wherein treating the metal-containing stream to recover the high nickel concentrate comprises filtering the high nickel concentrate from a metal-containing slurry utilizing a diatomaceous earth filter aid.

20. 20. The method of claim 19, further comprising adding lime to precipitate one or more metals from the metal-containing stream to produce a mixed hydroxide precipitate (MHP), gypsum, and a lithium-containing solution.

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