Method and system for upgrading reconstructed waste battery

Abstract

The present disclosure provides methods and systems for recycling and upgrading reconstituted waste battery cathode materials. In some embodiments, the method may include separating cathode material of a spent battery into a plurality of sets of particles, where a first set of the plurality of sets of particles includes first particles having a first size and a second set of the plurality of sets of particles includes second particles having a second size. The method further includes generating a first precursor solution using the first set of particles; generating a second precursor solution using the second set of particles; generating a first cathode material using the first precursor solution; and generating a second cathode material using the second precursor solution.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 374,569, filed on September 5, 2022, entitled “Methods and Apparatus for Upcycling Battery Cathode Materials,” which is incorporated herein by reference in its entirety. Statement Regarding Federally Funded Research

[0002] This invention was made with Government support under Grant No. DE-SC0020868 awarded by the Department of Energy. The Government has certain rights in this invention. Technical Field

[0003] The present application relates generally to battery recycling and more specifically to upcycling spent battery materials. Background Art

[0004] Lithium-ion batteries (LIBs) are widely used in many electronic devices, vehicles and other fields. Waste lithium-ion batteries may cause environmental problems and waste resources. End-of-life (EoL) lithium-ion batteries will become an important secondary source of materials for the production of new batteries. Reducing recycling costs and increasing recycling rates can significantly reduce the life cycle cost of lithium-ion batteries. This cost reduction can also prevent material shortages, reduce the environmental impact of producing new materials, and provide low-cost active materials for the manufacture of new lithium-ion batteries. With the significant increase in battery production in the next decade, primary waste generated during the production process will become a key source of global recycling operations. Currently, the industry mainly relies on high-temperature pyrometallurgical or hydrometallurgical methods to recycle lithium-ion batteries. These methods are usually followed by acid leaching or alkaline treatment processes to recover valuable elements such as lithium, nickel and cobalt. However, the reliance on high-temperature and high-intensity chemical processes leads to huge energy consumption, the generation of new chemical waste, and high operating costs. Innovative recycling technologies are essential to make lithium-ion battery recycling profitable without charging consumers for processing and to promote industry expansion. Direct recycling, which involves recovering and reusing battery components without changing their chemical structure, provides battery manufacturers with a more economical way to obtain recycled materials. This approach has the potential to reduce the cost of electric vehicle (EV) batteries, making them more attractive for recycling.

[0005] Direct recycling of lithium-ion batteries is gaining attention as a viable method. It can regenerate the positive and negative electrode materials without destroying them, and significantly reduce the use of energy and chemical reagents. However, the challenge is that the recycled materials are different from the current materials; the recycled electrode materials, which are usually 5 to 10 years old, may not meet the changing market needs considering the continuous improvement of electrode material performance and the emergence of new chemical systems.

[0006] Developing an effective upcycling process that can repair materials in a high-value form that can be sold again by manufacturers is critical to promoting the recycling of lithium-ion batteries. A profit-driven upcycling system can be aligned with market goals, including reducing battery costs and increasing the utilization of recycled battery materials.

[0007] During long-term cycling, many particles in the cathode material, such as LiNi x Co y Mn z O2 (lithium nickel cobalt manganese oxide, NCM) and LiNi x Co y Al z O2 (lithium nickel cobalt aluminum oxide, NCA) (where x+y+z=1), etc., often decompose into primary nanoparticles. This loss of secondary structure exposes new surfaces to the electrolyte, resulting in material degradation and subsequent electrochemical performance degradation. This performance degradation complicates the full recovery of electrochemical performance during standard hydrothermal or high-temperature lithium recharge processes, as these processes often fail to suppress the decomposition of these nanoparticles. Summary of the invention

[0008] The following is a simplified overview of the disclosure, intended to provide a basic understanding of some aspects of the disclosure. This overview is not a comprehensive review of the disclosure. It is neither intended to identify the key or core elements of the disclosure, nor to define any scope of a specific embodiment of the disclosure or any scope of the claims. Its sole purpose is to present some concepts of the disclosure in a simplified form as a prelude to a more detailed description that follows.

[0009] According to one or more aspects of the present disclosure, a method for upgrading and recycling waste batteries is provided. The method comprises: separating cathode materials of waste batteries into multiple groups of particles, wherein a first group of the multiple groups of particles comprises first particles having a first size, and a second group of the multiple groups of particles comprises second particles having a second size; using the first particles to generate a first precursor solution; using the second particles to generate a second precursor solution; using the first precursor solution to generate a first cathode material; and using the second precursor solution to generate a second cathode material.

[0010] In some embodiments, the first particles are microparticles and the second particles are nanoparticles.

[0011] In some embodiments, the first precursor solution includes at least one of a suspension comprising the first set of particles or a solution comprising the first set of particles.

[0012] In some embodiments, the first precursor solution further comprises LiOH, LiNO3, LiAc, Ni(NO3)2, Mn(NO3)2, Co(NO3)2, C2H2O4Ni, Ni(Ac)2, C2H2O4Mn, Mn(Ac)2, C 12 H 10 Mn3O 14 , at least one of C2H2O4Co, Co(Ac)2, and Al(NO3)3.

[0013] In some embodiments, the first precursor solution further includes a lithium precursor.

[0014] In some embodiments, the first precursor solution includes at least one dopant precursor.

[0015] In some embodiments, using the first precursor solution to generate the first cathode material includes: calcining the first precursor solution to generate first calcined particles; and performing surface engineering on the first calcined particles.

[0016] In some embodiments, generating the second cathode material using the second precursor solution includes: forming a plurality of microparticles using the second precursor solution; and calcining the plurality of microparticles to generate second calcined particles.

[0017] In some embodiments, forming the plurality of microparticles using the second precursor solution includes preparing micron-sized droplets using at least one of a spray granulation process or a spray drying process.

[0018] In some embodiments, using the second precursor solution to generate the second cathode material further comprises performing a surface engineering treatment on the second calcined particles.

[0019] In some embodiments, the second precursor solution includes at least one of a suspension containing the second set of particles or a solution containing the second set of particles.

[0020] In some embodiments, the second precursor solution includes LiOH, LiNO3, LiAc, Ni(NO3)2, Mn(NO3)2, Co(NO3)2, C2H2O4Ni, Ni(Ac)2, C2H2O4Mn, Mn(Ac)2, C 12 H 10 Mn3O 14, C2H2O4Co, Co(Ac)2 or Al(NO3)3.

[0021] In some embodiments, the second precursor solution includes a lithium precursor, wherein the lithium precursor includes at least one of LiOH, LiNO3, and LiAc.

[0022] In some embodiments, the second precursor solution includes a manganese precursor, wherein the manganese precursor includes Mn(Ac)2, Mn(NO3)2, C2H2O4Mn, C 12 H 10 Mn3O 14 Or at least one of Mn(NO2)2.

[0023] In some embodiments, the second precursor solution comprises a cobalt precursor, and wherein the cobalt precursor comprises at least one of Co(Ac)2, Co(NO3)2, C2H2O4Co, or Co(NO2)2.

[0024] In some embodiments, the second precursor solution includes an aluminum precursor, wherein the aluminum precursor includes at least one of Al[OCH(CH3)2]3, Al(N(CH3)2)3, Al[OCH(CH3)C2H5]3, (CH3)3Al or Al(NO3)3.

[0025] In some embodiments, the second precursor solution comprises one or more dopant precursors, wherein the dopant precursor comprises at least one of Al, Ti, Mg, Ca, Nb, Zr, W, Te, Mo, or F.

[0026] According to one or more aspects of the present disclosure, a system for upgrading and regenerating waste batteries is provided. The system may include: a particle separator configured to separate cathode materials of waste batteries into multiple groups of particles, wherein a first group of the multiple groups of particles contains first particles having a first size, and wherein a second group of the multiple groups of particles contains second particles having a second size; a precursor generator configured to: generate a first precursor solution using the first particles; and generate a second precursor solution using the second particles; and a battery upgrading component configured to: generate a first cathode material using the first precursor solution; and generate a second cathode material using the second precursor solution.

[0027] In some embodiments, the first particles are microparticles. In some embodiments, the second particles are nanoparticles.

[0028] In some embodiments, the battery upgrading component further includes a calcining component configured to calcine the first precursor solution to generate first calcined particles, and a surface engineering component configured to perform surface engineering treatment on the first calcined particles.

[0029] In some embodiments, the battery upgrading assembly further includes a particle reconstruction assembly configured to form a plurality of particles using a second precursor solution. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The present disclosure will be more fully understood through the detailed description given below and the accompanying drawings of various embodiments of the present disclosure. However, these drawings should not be understood to limit the present disclosure to specific embodiments, but are for explanation and understanding.

[0031] Figure 1 is a schematic diagram showing an exemplary system for upcycling spent batteries.

[0032] Figure 2 is a block diagram illustrating an exemplary process for generating cathode materials according to some embodiments of the present disclosure.

[0033] Figure 3A and Figure 3B is a block diagram illustrating an exemplary process for upcycling cathode materials according to some embodiments of the present disclosure.

[0034] Figure 4 and Figure 5 is a schematic diagram showing an exemplary particle generation reactor according to some embodiments of the present disclosure.

[0035] Figure 6 An exemplary calcining system according to some embodiments of the present disclosure is shown.

[0036] Figure 7 An exemplary surface engineering reactor according to some embodiments of the present disclosure is shown.

[0037] Fig. 8A , 8B 8C are flow charts illustrating an exemplary process for upcycling spent batteries according to some embodiments of the present disclosure.

[0038] Fig.9A is a scanning electron microscope (SEM) image of aged NCA cathode material.

[0039] Fig. 9B is the SEM image of the isolated damaged nanoparticles.

[0040] Fig. 9C is a SEM image of the particles of the upcycled NCA cathode material after morphological upgrading.

[0041] Fig.9D Shows Fig. 9C Cycling performance of upcycled NCA cathode materials and commercial NCA cathode materials.

[0042] Fig. 10A Shown is a comparison of X-ray diffraction (XRD) patterns of recycled polycrystalline NCM111 and upcycled single crystal NCM622 cathode materials.

[0043] Fig. 10B This is a SEM image of a single-crystal NCM622 cathode material upcycled from waste polycrystalline NCM111 cathode material.

[0044] Fig. 10C Shown are the first cycle charge-discharge curves of commercial multicrystalline NCM622 and upcycled single-crystalline NCM622 cathode materials at 0.1C.

[0045] Fig. 10D Shown is the cycling performance comparison of upcycled single-crystalline NCM622 and commercial multicrystalline NCM622 cathode materials at 1C.

[0046] Fig.11A is the SEM image of waste LFP nanoparticles.

[0047] Fig. 11B is the SEM image of the LFP cathode material after morphological upgrading.

[0048] Fig. 11C The particle size distribution of the upgraded LFP cathode material is shown.

[0049] Fig.11D The cycling performance comparison of spent LFP nanoparticles and upgraded LFP microparticle cathode materials is demonstrated.

[0050] Fig. 12A is a SEM image of the LMFP microparticle cathode material after morphology and chemical properties were upgraded.

[0051] Fig. 12B Represents the particle size distribution of the upgraded LMFP cathode material.

[0052] Fig. 12C XRD patterns of upcycled LFP and LMFP microparticle cathode materials are shown.

[0053] Fig.12D The second cycle charge-discharge curves of upcycled LFP and LMFP cathode materials are depicted. DETAILED DESCRIPTION

[0054] The present disclosure provides a mechanism (e.g., a system, a device, a method, etc.) for upgrading and regenerating waste batteries. The battery referred to in the present disclosure may be any electrical energy storage device. In some embodiments, the battery may be a lithium-ion battery (LIB). Waste batteries may include used and / or aged lithium-ion batteries, battery modules, battery packs, etc. As used in the present disclosure, "lithium-ion battery cathode material" refers to the material constituting the cathode of a lithium-ion battery, including but not limited to lithium cobalt oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese aluminum oxide, lithium manganese oxide, lithium iron phosphate, and lithium manganese iron phosphate.

[0055] Recycling lithium-ion batteries may involve discharging spent lithium-ion batteries and separating spent graphite using physical methods such as disassembly, crushing, screening, and other mechanical processes. The separated raw graphite anode material can be processed to produce recycled anode material (e.g., through direct regeneration of graphite) and / or upcycled anode material (e.g., by upgrading graphite anode material to graphite-based materials with additional functionalities required for energy and environmental applications). However, raw cathode materials obtained by separating raw cathode materials from other components of spent batteries may not meet battery industry standards due to the presence of impurities and structural defects.

[0056] According to one or more aspects of the present disclosure, a system for battery upgrading and recycling is provided. The system can process waste batteries and can produce regenerated and / or upgraded cathode materials that can be used for new battery electrodes. For example, the system can process the original cathode material of waste batteries (e.g., used and / or damaged lithium-ion battery cathode materials) and classify the cathode particles in the original cathode material according to size and / or morphology. Specifically, the system can separate cathode particles having a desired size, morphology, and crystallinity (also referred to as "complete cathode particles") from cathode particles lacking the desired size, morphology, and / or crystallinity (also referred to as "damaged cathode particles"). In some embodiments, the complete cathode particles may include microparticles (e.g., particles with a size between 1 micron and 300 microns). The damaged cathode particles may include nanoparticles (e.g., particles with a size between 1 nanometer and 1000 nanometers).

[0057] The system can generate upgraded cathode materials by processing the separated intact microparticles and damaged nanoparticles. For example, intact cathode particles can be regenerated and then surface coated to improve their stability. Damaged nanoparticles can be morphologically reconstructed and enhanced. During the morphological restoration process, damaged and fragmented particles can be converted into large particles (e.g., particles with a size of 1-100 microns) by forming a nanoparticle suspension or solution with a modified chemical composition and / or additional dopants, followed by a rapid gas phase treatment to form new particles with an upgraded chemical composition at low temperature. In addition, the nanoprecursors can serve as seeds for the synthesis of larger single crystalline particles.

[0058] Recycled cathode materials produced using the mechanisms described in the present disclosure may have desired morphology, composition, dopants, and crystallinity. The capacity of the upcycled cathode material may be comparable to the capacity of the original cathode material suitable for use in manufacturing electrodes for new batteries (e.g., lithium-ion batteries). The recycled cathode material may include, for example, lithium-ion battery cathode particles with upgraded morphology, lithium-ion battery cathode particles with upgraded chemical composition, desired dopants, lithium-ion battery cathode particles with upgraded crystal structure, etc.

[0059] By quickly separating particles and efficiently repairing damaged cathode particles, a considerable cathode material yield (between 95% and 98%) can be achieved. This method consumes much less energy than the traditional energy-intensive method of resynthesizing cathode materials from dissolved salt precursors. Such efficiency can significantly increase the adoption rate of lithium-ion battery recycling and regeneration processes. In addition, these recycled materials may be increasingly used in electric vehicles, stationary energy storage solutions, consumer electronics and other fields.

[0060] In the present disclosure, "desired morphology" can refer to a predetermined morphological characteristic of a particle. In some cases, the desired morphology refers to a desired shape and / or a desired size. In some cases, the desired morphology is substantially spherical.

[0061] In the present disclosure, "desired crystallinity" or "desired crystal structure" may refer to a predetermined crystal structure of a particle, which can generally be measured by X-ray diffraction (XRD) or other methods that can provide similar information. In some cases, the desired crystallinity described in the present disclosure is a layered structure with hexagonal symmetry, belonging to the R-3m space group (e.g., for lithium nickel cobalt manganese oxide (NCM), lithium nickel cobalt aluminum oxide (NCA), and lithium nickel cobalt manganese aluminum oxide (NCMA) chemical compositions). In some embodiments, the desired crystallinity is an ilmenite-derived structure, belonging to the orthorhombic Pnma space group (e.g., for lithium iron phosphate (LFP) and lithium iron manganese phosphate (LMFP) chemical compositions). In the present disclosure, "morphologically upgraded lithium-ion battery cathode particles" may refer to lithium-ion battery cathode particles whose morphology and / or particle size (e.g., nanoparticles) have been adjusted. For example, nanoparticles of used lithium nickel cobalt aluminum oxide (NCA) and lithium iron phosphate (LFP) lithium-ion battery cathode particles can be upgraded to micro-spherical lithium-ion battery cathode particles by morphological reconstruction.

[0062] In the present disclosure, "chemically upgraded lithium-ion battery cathode particles" may refer to lithium-ion battery cathode particles in which the stoichiometric ratio of lithium and other elements has been adjusted. For example, the stoichiometric ratio of NCM523 lithium-ion battery cathode particles can be adjusted by adding more lithium, nickel, and cobalt precursors, thereby upgrading them to NCM811 lithium-ion battery cathode particles. The stoichiometric ratio of LFP lithium-ion battery cathode particles can be adjusted by adding more lithium, manganese, and phosphorus precursors, thereby upgrading them to LMFP lithium-ion battery cathode particles.

[0063] In the present disclosure, "crystal structure upgraded lithium ion battery cathode particles" may refer to lithium ion battery cathode particles with adjusted crystal structure. For example, polycrystalline NCM111 lithium ion battery cathode particles may be adjusted by performing a second calcination process to upgrade them to single crystal NCM111 lithium ion battery cathode particles.

[0064] In this disclosure, "NCM" refers to lithium nickel cobalt manganese oxide, "NCA" refers to lithium nickel cobalt aluminum oxide, "NCMA" refers to lithium nickel cobalt manganese aluminum oxide, "LFP" refers to lithium iron phosphate, and "LMFP" refers to lithium manganese iron phosphorus oxide.

[0065] Figure 1 is a schematic diagram illustrating an exemplary system 100 for upcycling used batteries. Used batteries may include, for example, used and / or damaged lithium-ion batteries.

[0066] As shown, system 100 may include a pretreatment component 110, a particle separator 120, a precursor generator 130, a particle reconstruction component 140, a calcination component 150, a surface engineering component 160, and / or any other suitable component for upgrading and regenerating waste batteries according to the technology described in the present disclosure. Particle reconstruction component 140, calcination component 150 and surface engineering component 160 may be collectively referred to as a battery upgrade component 170. Without loss of generality, system 100 may include more or fewer modules. For example, two of the components may be merged into one component, or one of the components may be divided into two or more components.

[0067] The pretreatment component 110 can use an aqueous phase method to treat the original cathode material of the waste battery and generate a pretreated original cathode material 115. The original cathode material can be collected from the waste battery, for example, by discharging the waste battery and separating the original cathode material using a mechanical process (such as disassembly, crushing, screening, etc.). In some embodiments, the waste batteries may have the same chemical type (for example, containing the same cathode material). The original cathode material may include, for example, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese aluminum oxide, lithium iron phosphate, lithium iron manganese phosphate, etc.

[0068] In some embodiments, the pretreatment assembly 110 can purify the raw cathode material by fluidizing the gas-solid flow of the particle mixture, and can expose the particle mixture flowing through the plasma region to a non-equilibrium plasma. The plasma can maintain a predetermined power density for maintaining a predetermined exposure time and a predetermined solid-gas volume ratio to remove impurities.

[0069] The particle separator 120 can separate the pretreated cathode material 115 (e.g., purified cathode material) into multiple groups of particles of different sizes and / or morphologies. Each group can have particles of a specific size and / or size distribution. For example, the pretreated cathode material 115 can be divided into a first group of particles 125a and a second group of particles 125b. The first group of particles 125a can have a desired morphology and / or a desired particle size. The second group of particles 125b does not have the desired morphology or particle size of the first group of particles. More specifically, for example, the first group of particles 125a can have a desired shape and / or size, and can include complete spherical particles with a size between about 1 micron and about 100 microns. The second group of particles 125b does not have such a morphology or size, and can include nanoparticles with a size between about 1 nanometer and about 1000 nanometers.

[0070] The separation of the first group and the second group of particles can be achieved in a gas phase centrifugal process by controlling the aerodynamics of the air pressure and the airflow. In some embodiments, the particle separator 120 can utilize the gas phase centrifugal separation force in the vortex motion to separate the pretreated cathode material 115 into multiple groups of particles. In some embodiments, the particle separator 120 may include an axial cyclone separator coupled to the rotating gas under the condition of non-equilibrium low-temperature plasma discharge. The axial cyclone separator can utilize rapid particle separation in the gas phase to directly and selectively screen out complete cathode particles. The separation of complete cathode particles and damaged cathode particles can reduce the steps and costs of recycling and upgrading cathode materials.

[0071] The precursor generator 130 can generate one or more precursor solutions using the first group of particles 125a and / or the second group of particles 125b. In some embodiments, the precursor solution can include the particle group 125a and / or the particle group 125b, a solvent, a binder, etc., and form a suspension and / or solution with one or more chemical adjustment additives and one or more dopant precursors. Incorporating a small amount (0.01-5%) of dopants occupying transition metal (TM), lithium or oxygen sites into the cathode structure can improve the structure and electrochemical properties of the original cathode material.

[0072] Chemical adjustment additives may include chemicals containing nickel (Ni), manganese (Mn), cobalt (Co), phosphorus (P), or lithium (Li), and are used in contact with particles of used lithium-ion battery cathode materials to change the stoichiometric ratios of the elements in the lithium-ion battery cathode materials (e.g., NCM, lithium nickel cobalt aluminum oxide (NCA), lithium nickel cobalt manganese aluminum oxide (NCMA), lithium iron phosphate (LFP), lithium iron manganese phosphate (LMFP)). Examples of chemical adjustment additives may include LiOH, LiNO3, LiAc, Ni(NO3)2, Mn(NO3)2, Co(NO3)2, C2H2O4Ni, Ni(Ac)2, C2H2O4Mn, Mn(Ac)2, C 12 H 10 Mn3O 14 , C2H2O4Co, Co(Ac)2, Al(NO3)3, Al[OCH(CH3)2]3, Al(N(CH3)2)3, Al[OCH(CH3)C2H5]3, (CH3)3Al, etc.

[0073] Doping additives may include chemicals containing elements such as aluminum (Al), titanium (Ti), magnesium (Mg), calcium (Ca), niobium (Nb), zirconium (Zr), tungsten (W), tellurium (Te), molybdenum (Mo), fluorine (F), etc., to replace nickel (Ni), cobalt (Co), manganese (Mn) or oxygen (O). Doping strategies may play a vital role in improving the structure and electrochemical properties of original cathode materials (such as NCM). In a layered cathode structure with an R-3m space group, dopants occupy the sites of transition metals (TM), lithium or oxygen. Adding a small amount of one or more doping elements can effectively alleviate the volume change of the layered cathode during the phase change under high pressure conditions. On the other hand, adding one or more doping elements to the lithium site can play a key role, thereby improving the rate performance and structural stability during the cycle process. In addition, adding one or more doping elements to the lithium site can increase the energy density of the cathode material through the oxidation and / or reduction reaction of oxygen. The solvent may include, for example, water, ethanol, methanol, isopropanol, ethylene glycol, etc. The organic binder may include, for example, polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), and the like.

[0074] For example, the precursor generator 130 can generate a first precursor solution 135a using the first group of particles 125a. The first precursor solution 135a may also include a solvent, a binder, one or more chemical adjustment additives, one or more dopant precursors, etc. For another example, the precursor generator 130 can generate one or more second precursor solutions 135b using the second group of particles 125b. Each second precursor solution 135b may also include a solvent, a binder, one or more chemical adjustment additives, one or more dopant precursors, etc. The solvent may include, for example, water, ethanol, methanol, isopropanol, ethylene glycol, etc. The organic binder may include, for example, polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), etc. The chemical adjustment additive may include a lithium (Li) precursor, a manganese (Mn) precursor, a nickel (Ni) precursor, a cobalt (Co) precursor, an aluminum (Al) precursor, one or more dopant precursors, etc. The lithium precursor may include, for example, LiOH, LiNO3, LiAc, etc. Examples of nickel precursors may include Ni(Ac)2, Ni(NO3)2, C2H2O4Ni, NiBr2, etc. Examples of manganese precursors may include Mn(Ac)2, Mn(NO3)2, C2H2O4Mn, C 12 H 10 Mn3O 14, Mn(NO2)2, etc. Examples of cobalt precursors may include Co(Ac)2, Co(NO3)2, C2H2O4Co, Co(NO2)2, etc. Examples of aluminum precursors may include Al[OCH(CH3)2]3, Al(N(CH3)2)3, Al[OCH(CH3)C2H5]3, (CH3)3Al, Al(NO3)3, etc. The dopant precursor may include a chemical substance containing elements such as aluminum (Al), titanium (Ti), magnesium (Mg), calcium (Ca), niobium (Nb), zirconium (Zr), tungsten (W), tellurium (Te), molybdenum (Mo), or fluorine (F) instead of nickel (Ni), cobalt (Co), manganese (Mn), or oxygen (O). In some embodiments, the first precursor solution 135a may include a combination of Figure 2 In some embodiments, the second precursor solution 135b may include a combination of Figure 2 One or more precursor solutions 220, 230, 240, and 250 are described.

[0075] The particle reconstruction component 140 can generate particles 145 using the second precursor solution 135b. The particles can have a suitable size between 1 micron and 100 microns. For example, the particle reconstruction component 140 can synthesize the precursor powder by a droplet generation process. In some embodiments, the droplet generation process can involve the production of micron-sized droplets using a spray granulation process and / or a spray drying process. In some embodiments, the spray drying process and / or the spray granulation process can involve droplet generation and drying a suspension or solution of a lithium precursor solution containing suspended particles.

[0076] In some embodiments, a centrifugal droplet generation process may be used to generate micron-sized droplets. The centrifugal droplet generation process may involve using artificial gravity to generate droplets.

[0077] In some embodiments, the spray drying or spray granulation process can be adjusted to generate agglomerates of a suitable size between 1 micron and 100 microns. For example, the spray drying or spray granulation process can be adjusted to generate droplets of a given size, which are then dried into agglomerates of a desired size. In some embodiments, the droplet generator can be and / or include a centrifugal atomizer or a gas atomizer to generate droplets of a desired size (e.g., by adjusting nozzle design, liquid selection, gas flow and reactor design, etc.).

[0078] In some embodiments, the spray drying reactor or spray granulation reactor can use a drying gas to evaporate the liquid at a temperature between 50° C. and 400° C. The drying gas can be and / or include, for example, air, oxygen (O2), nitrogen (N2), argon (Ar), etc. In some embodiments, the dried microparticles have a desired morphology, which may be spherical or substantially spherical.

[0079] In some embodiments, the particle reconstruction assembly 140 may include a combination of Figure 4 The particle generation reactor 400 described herein and / or in combination Figure 5 A particle generation reactor 500 is described.

[0080] The calcination assembly 150 can calcine the first group of particles 125a, thereby generating the first calcined particles 155a and the microparticles 145 in situ. The calcination of the first group of particles 125a can re-lithiate the first group of particles 125a and generate the first calcined particles 155a. The calcination of the microparticles 145 can achieve re-lithiation, metal reduction, doping, crystallization, etc. of the microparticles 145, and generate second calcined particles 155b. For example, the calcination assembly 150 can calcine the first particles 125a and / or the microparticles 145 by fluidized bed pre-calcination and warm plasma calcination. During the fluidized bed pre-calcination process, the first elevated temperature decomposes the precursor compounds in the microparticles into oxides, which form strong binding forces to bind all the small nanoparticles inside the particles together to prevent agglomeration due to incomplete decomposition of the precursor. During the plasma calcination process, the second elevated temperature generated by the internal plasma discharge is applied to the pre-calcined particles to form calcined particles with a desired degree of crystallinity.

[0081] In some embodiments, the calcining assembly 150 may apply a first elevated temperature to the first group of particles 125a for pre-calcination. In some embodiments, the calcining assembly 150 may perform additional calcination using plasma at a second elevated temperature.

[0082] In some embodiments, the first elevated temperature and the residence time of the particles in the fluidized bed preheating chamber together control the porosity and morphology of the particles. The second elevated temperature and the temperature distribution along the particle flow path in the continuous plasma calcining zone can be controlled by various parameters to achieve the desired cathode material preparation.

[0083] In some embodiments, the first elevated temperature in the ebullating bed is between 200° C. and 700° C. In some embodiments, the second elevated temperature in the plasma reactor is between 600° C. and 2000° C.

[0084] In some embodiments, the calcining assembly 150 may undergo an additional calcining process to upgrade the calcined particles from a polycrystalline phase to a single crystalline phase. In some embodiments, the additional calcining process may be performed in a chamber with or without plasma.

[0085] In some embodiments, the calcining assembly 150 may include a combination of Figure 6 The calcining system 600.

[0086] The surface engineering component 160 can perform surface engineering treatment on the first calcined particles 155a and the second calcined particles 155b to achieve relithiation, repair, crystallization, carbon coating treatment and / or reconstruction of the calcined particles. The surface engineering component 160 can prepare the first cathode material 165a by treating the first calcined particles 155a, and prepare the second cathode material 165b by treating the second calcined particles 155b. The first cathode material 165a and the second cathode material 165b can be battery-grade cathode materials that can be used to manufacture cathode electrodes of new batteries.

[0087] In some embodiments, the surface engineering component 160 can be surface engineered using a fluidized bed spraying process. The spraying process can use the most advanced methods of existing batch processing for battery recycling to achieve continuous flow operation. When a solution or suspension is used for coating, the liquid can transport the solid components of the coating agent (also called a precursor) to the surface of the particles. Fluidized bed spraying may involve depositing a precursor on the first calcined particles 155a and / or the second calcined particles 155b, and then calcining in a second fluidized bed. The coating precursor may include a mixture of one or more coating agents, solvents, adhesives, etc. The coating agent may include, for example, carbon, LiF, Al2O3, TiO2, ZrO2, Li3PO4, LiNbO2, etc. Examples of solvents may include water, ethanol, methanol, isopropanol, ethylene glycol, etc. In some embodiments, the adhesive may include, for example, polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), etc. In some embodiments, the surface engineering component 160 may include a combination of Figure 7 The surface engineering reactor 700.

[0088] Figure 2 is a block diagram 200 illustrating an exemplary process for generating cathode material according to some embodiments of the present disclosure.

[0089] In some embodiments, the precursor solution 210 may be Figure 1 The precursor solution 210 may include a first set of particles 125a, a solvent, a binder, one or more lithium precursors, one or more dopant precursors, etc. The processing of the precursor solution 210 may generate a cathode material 210a.

[0090] In some embodiments, the precursor solution 220 may be Figure 1The precursor solution 220 may be processed by the particle reconstruction assembly 140, the online calcination assembly 150 and the surface engineering assembly 160 for morphological reconstruction. The precursor solution 220 may include a second set of particles, a solvent, a binder, one or more lithium precursors, one or more chemical adjustment additives, one or more dopant precursors, etc. The processing of the precursor solution 220 may generate a cathode material 220a.

[0091] In some embodiments, the precursor solution 230 may be processed by the particle reconstruction component 140, the calcination component 150, and the surface engineering component for chemical composition upgrading. The precursor solution 230 may include a second set of particles 125b, a solvent, a binder, one or more lithium precursors, one or more chemical adjustment additives, one or more dopant precursors, etc. The processing of the precursor solution 230 may generate a cathode material 230a.

[0092] In some embodiments, the precursor solution 240 may be processed by the particle reconstruction assembly 140 and the online calcination assembly 150 to achieve a crystal structure upgrade. For example, the particle reconstruction assembly 140 may use the precursor solution 240 to generate particles. The particles may then be processed by Figure 1 The calcined assembly 150 is calcined. The calcined particles may be subjected to an additional calcination process to generate a cathode material 240a. The precursor solution 240 may include a second set of particles 125b, a solvent, a binder, one or more lithium precursors, etc. The precursor solution 240 may or may not include a chemical adjustment additive. The precursor solution 240 may or may not include a dopant precursor.

[0093] In some embodiments, the precursor solution 250 may be processed by the particle reconstruction component 140, the calcination component 150, and the surface engineering component 160 to prepare the cathode material 250a. The precursor solution 250 may include the second group of particles 125b, a metal leachate, a solvent, a binder, a lithium precursor containing a chemical adjustment additive, etc. The precursor solution 250 may include one or more nickel precursors, manganese precursors, cobalt precursors, lithium precursors, dopant precursors, etc.

[0094] Figure 3A and Figure 3B is a schematic diagram showing example particles of cathode material according to some embodiments of the present disclosure.

[0095] like Figure 3A As shown, the raw cathode material 105 may be purified (e.g., by Figure 1 and separated into a first group of particles 125a and a second group of particles 125b (e.g., by Figure 1The first calcined particles 155a may be generated by relithiating and calcining the first group of particles 125a (e.g., by Figure 1 The first cathode material 165a can be generated by surface engineering (e.g., surface coating) the first calcined particles 155a (e.g., by Figure 1 The first set of particles 125a can be regenerated in a subsequent relithiation step.

[0096] The size of the second group of particles 125b is generally in the range of 50-1000 nanometers. As described in more detail in the present disclosure, the second particles 125b can be restored to large particles (5-15 microns) in a morphology recovery process that only involves the formation of a nanoparticle suspension in water, followed by a rapid gas phase treatment at a low temperature of 40 to 400°C.

[0097] Combined with rapid particle separation and rapid repair of damaged particles, a high overall cathode material yield (95%-98%) can be achieved with much lower energy consumption compared to the energy-intensive cathode material resynthesis process from dissolved salt precursors. This greatly accelerates the market penetration of lithium-ion battery recycling and regeneration, as well as the use of recycled materials for electric vehicles and stationary energy storage.

[0098] Reference Figure 3B The particles 345a can be generated by adding one or more lithium precursors, carbon precursors, and dopant precursors to the second group of particles 125b and upgrading the morphology of the second group of particles 125b (e.g., using Figure 1 The calcined particles 355a can be prepared by using the precursor generator 130 and particle reconstruction assembly 140 in the embodiment of the present invention. Figure 1 The calcination assembly 150 in the embodiment of the present invention calcines the particles 345a to generate the particles 345a. The calcination of the particles 345a can achieve relithiation, element doping and carbon coating of the particles 345a. The upcycled cathode material 365a can be generated by surface engineering (e.g., surface coating) the calcined particles 355a (e.g., by Figure 1 Surface engineering components in 160).

[0099] The particles 345b can be generated by adding one or more lithium precursors, one or more dopant precursors, M precursors, P precursors, C precursors, etc. to the second group of particles 125b, and upgrading the morphology and chemical composition of the second group of particles 125b (e.g., by Figure 1 The calcined particles 355b can be prepared by using the precursor generator 130 and particle reconstruction assembly 140 in the embodiment of the present invention. Figure 1The calcination assembly 150 in the embodiment of the present invention calcines the particles 345b to generate the particles 345b. The calcination of the particles 345b can achieve relithiation, metal reduction and carbon coating of the particles 345b. The upcycled cathode material 365b can be generated by surface engineering (e.g., surface coating) the calcined particles 355b (e.g., by Figure 1 Surface engineering components in 160).

[0100] The particles 345c can be generated by adding one or more lithium precursors, M precursors, etc. to the second group of particles 125b and reconstructing the second group of particles 125b (e.g., using Figure 1 The calcined particles 355c can be prepared by using the precursor generator 130 and particle reconstruction assembly 140 in the embodiment of the present invention. Figure 1 Calcination of particles 345b may achieve relithiation, metal reduction, and doping of particles 345c. Upcycled cathode material 365c may be generated by subjecting calcined particles 355c to an additional calcination process (e.g., using Figure 1 Calcination assembly 150).

[0101] The particles 345d can be generated by adding one or more lithium precursors, M precursors, P precursors, C precursors, etc. to the second group of particles 125b and upgrading the morphology, chemical composition and doping of the second particles 125b (for example, using Figure 1 The calcined particles 355d can be prepared by using the precursor generator 130 and particle reconstruction assembly 140 in the embodiment of the present invention. Figure 1 The calcination assembly 150 in the embodiment of the present invention calcines the particles 345d to generate the particles 345d. The calcination of the particles 345d can achieve crystallization, doping and carbon coating of the particles 345d. The upcycled cathode material 365d can be generated by surface engineering (e.g., surface coating) the calcined particles 355d (e.g., using Figure 1 Surface engineering components in 160).

[0102] Figure 4 and Figure 5 is a schematic diagram showing exemplary particle generation reactors 400 and 500 according to some embodiments of the present disclosure.

[0103] like Figure 4 As shown, particle generation reactor 400 may include a droplet generator 410, a chamber 420, inlets 431 and 433, a powder classification unit 440, and / or any other suitable components for generating particles using the spray drying process described in the present disclosure.

[0104] The precursor solution may be provided to the chamber 420 through the inlet 431. The droplet generator 410 may include one or more atomizing nozzles and / or any other suitable mechanism (e.g., a centrifugal droplet generation process) that can generate micron-sized droplets using the precursor. In the chamber 420, the precursor may be pumped through the atomizing nozzle under high pressure. At the outlet of the droplet generator, the precursor is atomized into micron-sized droplets. At the same time, a stream of hot carrier gas may be introduced from the bottom of the chamber 420 through the inlet 433, thereby forming a vortex from the bottom to the top of the chamber 420. The vortex may generate a temperature gradient so that the temperature at the bottom of the chamber is higher and the top is relatively lower. The droplet size generated by the particle generation reactor 400 may be controlled by adjusting the spray parameters, such as pressure, flow rate, nozzle geometry, etc. The particles generated in the chamber 420 are provided to the powder classification unit 440 for classification. The powder classification unit 440 may include an air classification system or any other suitable system (e.g., screening) for classifying particles by size. The powder classification unit 440 classifies the particles generated in the chamber 420 into particles 445a having a desired size and particles 445b having a non-desired size. The particles 445a having a desired size can be collected for further processing. The particles 445b having a non-desired size can be recovered and reused as a precursor raw material.

[0105] Reference Figure 5 The particle generation reactor 500 may include a droplet generator 510, a chamber 520, inlets 531 and 533, a powder classification unit 540, one or more filters 550, an exhaust system 560, and / or any other suitable components for generating particles using the spray granulation process described in the present disclosure.

[0106] The precursor solution (e.g., a solution or suspension containing solids) can be sprayed by the droplet generator 510 to form droplets in the fluidized bed system. The droplet generator 510 may include one or more atomizing nozzles and / or any other suitable mechanism for generating micron-sized droplets using a precursor (e.g., a centrifugal droplet generation process). At the same time, a stream of hot carrier gas can be introduced from the bottom of the chamber 520 through the inlet 533 to form a vortex from the bottom to the top of the chamber 520.

[0107] The rapid heat exchange between the hot gas phase and the micron-sized droplets results in rapid evaporation of the liquid and the formation of the initial nuclei of nanoparticles and / or microparticles. As more droplets are introduced into the system, they come into contact with the initial nuclei. As the surrounding liquid evaporates, the size of the nuclei increases, forming larger particles. This process continues within the fluidized bed, allowing the particles to grow layer by layer. This layer-by-layer accumulation can produce high-density particles.

[0108] The particles produced in the chamber 520 will be provided to the powder classification unit 540 for classification. The powder classification unit 540 may include an air classification system or any other suitable system (e.g., screening) that can classify the particles by size. The powder classification unit 540 will classify the particles produced in the chamber 520 into particles of a desired size and particles that do not have a desired size. The filter 550 may include a filtration system that can physically separate solid particles from a solid-gas mixture. The exhaust system 560 can guide the reaction exhaust gas away from the controlled reaction area. The particles of the desired size can be collected for further processing, and the particles that do not have the desired size can be recycled and reused as precursor raw materials.

[0109] Figure 6 An exemplary calcination system 600 according to some embodiments of the present disclosure is shown. The calcination system 600 may include an ebullated bed system 610 and a plasma calcination system 620. The ebullated bed system 610 may include a chamber 613, a filter 614, and an exhaust device 615. The plasma calcination system 620 may include a power supply 622, a water wall 623, a rapid cooling zone 624, and a laminar flow zone 625.

[0110] The power supply 622 can be any suitable electrical device that can power an electrical load in a plasma reaction. The power supply can convert the current from the power supply into the correct voltage, current and frequency to power the load. The water-cooled wall 623 and the rapid cooling zone 624 serve as cooling components to protect the calcining system 600 from high temperatures. The laminar flow zone 625 can achieve a fluid flow in which the gas / solid fluid flows smoothly or along a regular path.

[0111] A precursor comprising cathode material particles (e.g., Figure 1 The first precursor solution 135a and / or particles 145 in the fluidized bed system 610 can be provided to the fluidized bed system 610. In the fluidized bed, a high temperature gas flow 612 can enter the fluidized bed chamber 613 from the bottom of the fluidized bed chamber 613. The hot gas flow can trigger the decomposition of the precursor compounds in the particles into oxides or phosphates, which can form a strong binding force to bind the small nanoparticles inside the particles together and prevent agglomeration due to incomplete segmentation of the precursor. The decomposition temperature and residence time of the particles in the fluidized bed chamber can control the porosity and morphology of the particles. The continuous gas flow can guide the pre-calcined particles 621 to the warm plasma reactor. The internal plasma discharge can raise the particle temperature to 1500-2000°C in a short time and form molten micro-droplets. In this online plasma calcination area, the plasma temperature and the temperature distribution along the particle flow path will be controlled by various parameters to obtain a final well-calcined material. Compared with batch calcination in a static furnace, the relatively large surface area of ​​the entrained powder allows full calcination to be completed in a greatly shortened time.

[0112] After in-situ plasma calcination, there are two ways to process the calcined particles. In the first way, the calcined particles can be collected for subsequent addition processing. In the second way, the hot gas and powder are discharged from the bottom of the heating zone, which may be drawn into the high flow rate area of ​​the system. The flow rate of the carrier gas drawn into the high flow rate area of ​​the system is much higher than the flow rate flowing through the spray drying chamber, resulting in heat loss to a large amount of gas, thereby causing the particle temperature to drop sharply. Through this high-speed gas flow, the calcined particles are transported upward and enter the surface engineering reactor described in the present disclosure.

[0113] Figure 7 An exemplary surface engineering reactor 700 according to some embodiments of the present disclosure is shown. The surface engineering reactor 700 may include a spray system 710 and an ebullient bed system 750. The spray system 710 may include a droplet generator 713, a chamber 715, a filter 717, and an exhaust system 719. The ebullient bed system 750 may include an ebullient bed 753, a powder collector 755, and an exhaust system 757.

[0114] The droplet generator 705 may include one or more nozzles and / or any other suitable mechanism for generating a spray of the coating precursor 701. The calcined particles generated by the calcination system 600 may be coated with the precursor in the chamber 715. The carrier gas hot gas stream 703 may be introduced into the chamber 715 through the bottom of the chamber 715. The precursor solution sprayed into the chamber 715 may cause the particles to generate turbulence and fully mix, thereby forming a uniform coating on the surface of the calcined particles. The carrier gas separated from the previously entrained powder may leave the chamber 715 and directly enter the exhaust system 719. After the particles are coated with the precursor, the coated particles may be transported to the fluidized bed 753 (also referred to as the second fluidized bed). The high temperature gas stream 707 may enter the fluidized bed system 750 from the bottom of the chamber 751, and may decompose the coating precursor on the particles into oxides to form a uniform surface coating. The coated particles may be collected at the powder collector 755.

[0115] The spray coating process in the surface engineering reactor 700 can form an optimal surface coating on the calcined particles. When a solution or suspension is used for coating, the liquid serves to transport the solids to the particle surface. The coating technology described in the present disclosure can provide the particles with an optimal residence time in the surface engineering reactor 700, thereby ensuring excellent coating quality.

[0116] Fig. 8A is a flow chart of an exemplary process 800 for upgrading and recycling used batteries according to some embodiments of the present disclosure. The process 800 may be used Figure 1 System 100 in Figure 4 The particle generation reactor 400, Figure 5The particle generation reactor 500, Figure 6 The calcining system 600 and / or Figure 7 This is achieved by the surface engineering reactor 700.

[0117] In step 810, cathode materials of used batteries may be separated into a plurality of groups of particles having different sizes and / or shapes. For example, a first group of particles may include first particles having a first size, and a second group of particles may include second particles having a second size. The first particles and the second particles may be combined. Figure 1 The cathode material can be combined with the first particle 125a and the second particle 125b. Figure 1 The particle separator 120 performs separation.

[0118] At step 820, a first precursor solution may be generated using the first set of particles. The first precursor solution may include at least one of a suspension containing the first set of particles or a solution containing the first set of particles. In some embodiments, the first precursor solution may include LiOH, LiNO3, LiAc, Ni(NO3)2, Mn(NO3)2, Co(NO3)2, C2H2O4Ni, Ni(Ac)2, C2H2O4Mn, Mn(Ac)2, C 12 H 10 Mn3O 14 , C2H2O4Co, Co(Ac)2, or Al(NO3)3. In some embodiments, the first precursor solution may include a lithium precursor and a dopant precursor. In some embodiments, the dopant precursor may include one or more aluminum dopant precursors, magnesium dopant precursors, titanium dopant precursors, calcium dopant precursors, niobium dopant precursors, zirconium dopant precursors, tungsten dopant precursors, tellurium dopant precursors, fluorine dopant precursors, or molybdenum dopant precursors. The first precursor solution may be composed of a combination of Figure 1 The precursor generator 130 is used to generate.

[0119] At step 830, a second precursor solution may be generated using the second set of particles. The second precursor solution may include at least one of a suspension containing the second set of particles or a solution containing the second set of particles. In some embodiments, the second precursor solution may include LiOH, LiNO3, LiAc, Ni(NO3)2, Mn(NO3)2, Co(NO3)2, C2H2O4Ni, Ni(Ac)2, C2H2O4Mn, Mn(Ac)2, C 12 H 10 Mn3O 14, C2H2O4Co, Co(Ac)2, Al(NO3)3 or at least one of the dopant precursors. In some embodiments, the second precursor solution may include one or more lithium precursors, manganese precursors, cobalt precursors, aluminum precursors, etc. In some embodiments, the second precursor solution may include one or more aluminum dopant precursors, titanium dopant precursors, magnesium dopant precursors, calcium dopant precursors, niobium dopant precursors, zirconium dopant precursors, tungsten dopant precursors, tellurium dopant precursors, fluorine dopant precursors or molybdenum dopant precursors. The second precursor solution may be composed of a combination of Figure 1 The precursor generator 130 is used to generate.

[0120] At step 840, a first precursor solution may be used to generate a first cathode material. Figure 8B As shown, in step 841, the first precursor solution may be calcined to generate first calcined particles. The calcination of the first precursor solution may relithiate the first particles and perform doping. More specifically, for example, as combined with Figure 1 to Figure 2 As described above, the calcining assembly 150 may generate the first calcined particles 155a using the first precursor solution 135a.

[0121] At step 843, the first calcined particles may be subjected to surface engineering treatment. For example, Figure 1 and Figure 7 The first cathode material may be a combination of Figure 1 and Figure 2 The first cathode material 165a.

[0122] At step 850, a second precursor solution may be used to generate a second cathode material. Figure 8C As shown, a second precursor solution may be used to form a plurality of microparticles in step 851. More specifically, for example, as combined Figure 1 As described above, the particle reconstruction component 140 can use the second precursor solution 135b to generate particles 145. The particles can include a combination of Figure 3B The one or more calcined particles 355a, 355b, 355c and 355d.

[0123] At step 853, the plurality of microparticles may be calcined to generate second calcined particles. More specifically, for example, as combined Figure 1 As described above with reference to FIG. 3 , the calcining assembly 150 may use the second precursor solution 135 b to generate the second calcined particles 155 b .

[0124] At step 855, the second calcined particles may be subjected to a surface engineering treatment. The second cathode material may be and / or include Figure 1The second cathode material 165b in Figure 3B Upcycled cathode materials 365a, 365b, 365c, 365d.

[0125] Fig.9A Shown is a scanning electron microscope (SEM) image of an aged NCA lithium-ion cathode material, where severe particle cracking can be observed. Fig. 9C Shown are morphologically reconstructed NCA lithium-ion battery cathode material particles, the particles being derived from Fig. 9B The broken nanoparticles shown in the figure were obtained under optimized conditions. These secondary particles maintain a uniform spherical morphology with a tightly packed structure. Inside these particles, the primary particles are evenly distributed across their cross-section, highlighting their compactness. Particle size analysis shows that 50% of these particles have a diameter of less than 13 microns. The formation of these micron-sized spherical secondary particles can significantly increase the tap density, which is very beneficial for the preparation of electrodes. The electrochemical performance of the developed NCA cathode material was evaluated using a half-cell button cell. Fig.9D As shown, the reconstructed NCA cathode material shows comparable cycling performance to that of the commercial NCA sample.

[0126] Compared with polycrystalline particles, layered NCM materials made of single-crystal particles without grain boundaries can reduce inter-particle stress and are less prone to particle cracking at high charge states. In addition, single-crystal NCM particles are more resistant to corrosion by harmful electrolytes. Fig. 10B Shown is the SEM image of single-crystalline NCM622 regenerated from damaged NCM111 polycrystalline particles through a specific annealing process. Fig. 10A The X-ray diffraction (XRD) patterns shown in the figure confirm the crystal phase of layered single-crystalline NCM622. Half-cells were assembled using commercial polycrystalline NCM622 (PS-NCM622) cathodes and recycled single-crystalline NCM622 (SC-NCM622) cathodes. Fig. 10C and Fig. 10D As shown, the regenerated SC-NCM622 is slightly better than the commercial PS-NCM622 in terms of initial discharge specific capacity, first coulombic efficiency and cycle performance.

[0127] Fig.11A Aged and purified lithium iron phosphate (LFP) cathode material containing nanoparticles is shown. Using a carefully selected precursor suspension (including spent lithium iron phosphate nanoparticles, lithium source, solvent and binder), spray-dried LiFePO4 particles were annealed at 700 degrees Celsius in an argon environment for 5 hours. Fig. 11B As shown. Fig. 11CAs shown in Figure 2, all of these particles maintained a spherical morphology with a D50 of 9.7 μm. Comparison of the specific discharge capacity and cycling performance of the original LFP nanoparticle cathode material with that of the regenerated LFP microparticle cathode material at a charge and discharge rate of C / 5 in a half-cell (relative to Li / Li+) is shown in Figure 2. Fig.11D shown. Fig.11D The results show that the discharge capacity of the regenerated LFP cathode material (150 mAh / g) is significantly higher than that of the original lithium iron phosphate cathode material (134 mAh / g), indicating that the lithium ions in the crystal structure of the spent LFP have been fully restored.

[0128] For the regeneration of lithium iron manganese phosphate (LMFP), in addition to lithium, additional manganese and phosphorus sources are essential to maintain the chemical balance, targeting LiMn 0.5 Fe 0.5 PO4. Similar to the regenerated LFP particles, the regenerated LMFP particles are spherical, e.g. Fig. 12A The primary particles are tightly packed, leaving very little space, while the secondary particles are highly spherical with an average diameter of 9.67 microns (D50), as shown in Figure 2. Fig. 12B shown. Fig. 12C The XRD characterization results of the regenerated LFP and LMFP particles are given. The diffraction patterns of both samples are in good agreement with those of lithium manganese phosphate (LiMnPO4) and lithium iron phosphate (LiFePO4), and both belong to the Pmnb (62) space group. It is noteworthy that no impurity phases were detected, which highlights the high purity of the regenerated products. The electrochemical properties of the regenerated LFP and LMFP cathode materials are shown in Figure 2. Fig.12D Although the discharge capacities of the two samples are similar, both around 150 mAh / g, the energy density of the regenerated LMFP cathode shows a higher energy density compared to the LFP, from 500 Wh / kg to 600 Wh / kg, an increase of about 20% due to the higher operating voltage.

[0129] For ease of explanation, the method of the present disclosure is described and presented as a series of steps. However, the steps according to the present disclosure may occur in various orders and / or simultaneously, and may also occur with other steps not proposed and described herein. In addition, not all illustrated steps are necessary for implementing the method according to the disclosed subject matter. In addition, those skilled in the art will understand and appreciate that these methods may also be represented as a series of interrelated states through state diagrams or events.

[0130] In some embodiments, the terms "approximately," "approximately," and "substantially" may mean within ±20% of a target size; in some embodiments, within ±10% of a target size; in some embodiments, within ±5% of a target size; and in some embodiments, within ±2%. The terms "approximately" and "approximately" may include the target size itself.

[0131] In the above description, many details are described. However, it is apparent that the present disclosure can be implemented without these specific details. In some cases, in order to avoid obscuring the present disclosure, well-known structures and devices are shown in block diagram form rather than in detail.

[0132] The terms “first”, “second”, “third”, “fourth”, etc. used in this document are used as labels to distinguish different elements and do not necessarily have sequential meanings according to their numerical sequences.

[0133] The word "example" or "exemplary" as used herein means as an example, instance or illustration. Any aspect or design described herein as "example" or "exemplary" is not necessarily to be understood as being more preferred or advantageous than other aspects or designs. On the contrary, the use of the words "example" or "exemplary" is intended to present concepts in a concrete way. In this application, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or". That is, unless otherwise specified or obvious from the context, "X includes A or B" is intended to mean any natural inclusive arrangement. That is, if X includes A; X includes B; or X includes both A and B, then in any of the above cases, "X includes A or B" is established. In addition, the articles "one" and "some" used in this application and the appended claims should generally be interpreted as "one or more", unless otherwise specified or obvious from the context that it is directed to the singular form. In this specification, reference to "one embodiment" or "an embodiment" means that the specific features, structures or characteristics described in connection with the embodiment are included in at least one embodiment. Thus, the appearances of the phrases "one embodiment" or "an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment.

[0134] Although many modifications and variations of the present disclosure will undoubtedly become apparent to those of ordinary skill in the art after reading the above description, it should be understood that any particular embodiment shown and described by way of example is in no way intended to be considered limiting. Therefore, reference to details of various embodiments is not intended to limit the scope of the claims, which themselves merely recite those features that are considered to constitute the present disclosure.

Claims

1. A method for upgrading and recycling waste batteries, the method comprising: Separating the cathode material of the used battery into a plurality of groups of particles, wherein a first group of the plurality of groups of particles includes first particles having a first size, and a second group of the plurality of groups of particles includes second particles having a second size; generating a first precursor solution using the first particles; generating a second precursor solution using the second particles; generating a first cathode material using the first precursor solution; and A second cathode material is generated using the second precursor solution. The method according to claim 1 , wherein the first particles are microparticles and the second particles are nanoparticles. 3 . The method of claim 1 , wherein the first precursor solution comprises at least one of a suspension including the first particles or a solution including the first particles.

4. The method according to claim 3, wherein the first precursor solution further comprises LiOH, LiNO3, LiAc, Ni(NO3)2, Mn(NO3)2, Co(NO3)2, C2H2O4Ni, Ni(Ac)2, C2H2O4Mn, Mn(Ac)2, C 12 H 10 Mn3O 14 , C2H2O4Co, Co(Ac)2 or Al(NO3)3.

5. The method of claim 3, wherein the first precursor solution comprises one or more dopant precursors, wherein the dopant precursor comprises at least one of aluminum (Al), titanium (Ti), magnesium (Mg), calcium (Ca), niobium (Nb), zirconium (Zr), tungsten (W), tellurium (Te), molybdenum (Mo) or fluorine (F). The method according to claim 3 , wherein the first precursor solution further comprises a lithium precursor.

7. The method of claim 1, wherein generating the first cathode material using the first precursor solution comprises: calcining the first precursor solution to generate first calcined particles; and The first calcined particles are subjected to surface engineering treatment.

8. The method of claim 1, wherein generating a second cathode material using the second precursor solution comprises: forming a plurality of microparticles using the second precursor solution; and The plurality of microparticles are calcined to generate second calcined particles. 9 . The method of claim 8 , wherein forming the plurality of microparticles using the second precursor solution comprises generating micron-sized droplets using at least one of a spray granulation process or a spray drying process.

10. The method according to claim 9, wherein generating a second cathode material using the second precursor solution further comprises: The second calcined particles are subjected to surface engineering treatment. 11 . The method of claim 1 , wherein the second precursor solution comprises at least one of a suspension containing the second particles or a solution containing the second particles.

12. The method according to claim 11, wherein the second precursor solution comprises LiOH, LiNO3, LiAc, Ni(NO3)2, Mn(NO3)2, Co(NO3)2, C2H2O4Ni, Ni(Ac)2, C2H2O4Mn, Mn(Ac)2, C 12 H 10 Mn3O 14 , C2H2O4Co, Co(Ac)2 or Al(NO3)3.

13. The method according to claim 12, wherein the second precursor solution comprises a lithium precursor, wherein the lithium precursor comprises at least one of LiOH, LiNO3, and LiAc.

14. The method according to claim 12, wherein the second precursor solution comprises a manganese precursor, wherein the manganese precursor comprises Mn(Ac)2, Mn(NO3)2, C2H2O4Mn, C 12 H 10 Mn3O 14 Or at least one of Mn(NO2)2.

15. The method of claim 12, wherein the second precursor solution comprises a cobalt precursor, and wherein the cobalt precursor comprises at least one of Co(Ac)2, Co(NO3)2, C2H2O4Co, or Co(NO2)2.

16. The method of claim 12, wherein the second precursor solution comprises an aluminum precursor, wherein the aluminum precursor comprises at least one of Al[OCH(CH3)2]3, Al(N(CH3)2)3, Al[OCH(CH3)C2H5]3, (CH3)3Al, or Al(NO3)3.

17. The method of claim 12, wherein the second precursor solution comprises one or more dopant precursors, wherein the dopant precursor comprises at least one of Al, Ti, Mg, Ca, Nb, Zr, W, Te, Mo, or F.

18. A system comprising: A particle separator configured to separate cathode materials of spent batteries into a plurality of groups of particles, wherein a first group of the plurality of groups of particles comprises first particles having a first size, and a second group of the plurality of groups of particles comprises second particles having a second size; The precursor generator is configured as follows: generating a first precursor solution using the first particles; and generating a second precursor solution using the second particles; and The battery upgrade kit is configured as follows: generating a first cathode material using the first precursor solution; and A second cathode material is generated using the second precursor solution.

19. The system of claim 18, wherein the first particles are microparticles and the second particles are nanoparticles.

20. The system of claim 18, wherein the battery upgrade component further comprises: a particle reconstruction assembly configured to form a plurality of particles using the second precursor solution; The calcination assembly is configured to: calcining the first precursor solution to generate first calcined particles; and calcining the plurality of microparticles to produce second calcined particles; and The surface engineering component is configured to perform surface engineering treatment on the first calcined particles.

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