How to recycle lithium-ion batteries

Abstract

A method for recycling lithium ion batteries is provided. The present invention relates to a highly efficient and environmentally friendly method for recycling lithium ion batteries, which comprises disassembling the lithium ion batteries to obtain large quantities and high quality of components of the lithium ion battery cells, such as anodes, containing their respective active material compositions, for further material recovery by hydrometallurgical processes.

Description

[Technical field]

[0001] The present invention relates to the recycling of lithium ion batteries, particularly but not exclusively for E-mobility applications such as electric vehicles, and provides a highly efficient method for recycling lithium ion batteries, achieving high recovery rates through effective pre-treatment and hydrometallurgical procedures. [Background technology]

[0002] Currently, lithium-ion batteries (LiBs) are considered to be a very reliable and efficient technology for sustainable and green (electrical) energy storage systems for several reasons, including their high energy density, high power per battery weight, and the ability to be lighter and smaller than other rechargeable batteries. New research and manufacturing methods for lithium-ion batteries have resulted in increased storage capacity, faster charging speeds, and longer overall life spans. Meanwhile, new developments and innovations in this field are highly dependent on the availability and price of virgin raw materials, which are mainly mined in non-European and non-Mediterranean countries by foreign companies. Moreover, the raw materials required for the production of new lithium-ion batteries are only available in limited quantities due to their finiteness and low reserves, so the risk of raw material shortages and demand exceeding supply is already a reality today (e.g., cobalt, lithium, nickel, etc.).

[0003] Furthermore, from a sustainability perspective, raw materials such as cobalt (Co), nickel (Ni), manganese (Mn) and lithium (Li) are extracted from natural minerals, which requires mining operations in vast areas, sometimes agricultural or residential areas, and chemically hazardous processing. These extraction operations contribute significantly to environmental and air pollution with heavy metals and consume large amounts of water. Also, the use of high-throughput machines for extraction and processing leads to greenhouse gas emissions. As a result, as the global demand for lithium-ion battery manufacturing increases, environmentally sustainable and economically viable recycling technologies are becoming a key focus area. Therefore, alternative material sources for lithium-ion batteries are gaining attention and importance in modern society, and in this case, recycling is one of the key technologies involved.

[0004] State-of-the-art lithium-ion battery recycling considers the recycling of lithium-ion battery anode active materials such as lithium nickel manganese cobalt oxide (NMC), lithium cobalt oxide (LCO), lithium manganese oxide (LMO), lithium nickel oxide (LNO) and other compositions, but other important components of the lithium-ion battery pack are not considered, not properly recovered, or are destroyed. Recycling and recovery are primarily focused on obtaining anode active materials due to the economically overwhelming weight of anode materials. Recovery of lithium-ion battery materials can be done by recovering the anode material composition as a combination of products and compounds of anode active elements such as nickel, cobalt, manganese, and lithium in various stoichiometric ratios. This powder mixture of active material compounds with various chemical element contents is accumulated and is often referred to as "black mass" where iron, phosphorus, aluminum, copper, and plastic impurities may still be present. It is important to emphasize that the initial cathode active materials, e.g. nickel-manganese-cobalt, lithium-cobalt oxide, lithium-iron-phosphate (LFP), are not recycled and recovered as chemically pure individual elements, but as collective chemical products / compounds that contain some degree of impurity as precursor materials. Some recycling procedures recover elements, but the recycling efficiency reaches less than 80% (based on optimistic assumptions) when comparing the mass of the feed material with the mass of the discharged material (feed mass vs. recovered mass of discharged material). Cathode materials and other packaging materials (e.g. metal current collectors) are also recovered, but mostly in the form of mixed milled powders, with high impurity levels and requiring additional purification steps.

[0005] The core process of current recycling methods is solved around "shredding / grinding" as a mechanical pretreatment process to reduce the volume by crushing lithium-ion batteries into small pieces and obtain up to 75% of the mass of active materials implemented in lithium-ion batteries. For this, lithium-ion battery modules (including cases, plastics, adhesives, connectors, battery cells, etc.) are shredded and reduced to micrometer particle sizes before separating the heterogeneous materials of the received powder mixture into active materials, for example, anode, cathode, and current collector materials. During this process, the materials are exposed to high stresses, temperatures, and forces, and some particles are incinerated, destroyed, or irreversibly changed, making the recycling of these materials impossible. In most cases, the mechanical pretreatment is completed in at least two grinding process steps instead of a single grinding step, but some recycling methods have not shown any improvement even with the three grinding process steps available in the industry. In addition, complex sieving, washing, and post-treatment processes are required to obtain processable black mass after grinding.

[0006] Current recycling methods consider the following steps for the recovery of black chunks:

[0007] Crushing as a pretreatment followed by mineral acid leaching and highly complex separation processes: -Discharge the lithium-ion battery pack.

[0008] -Open the lithium-ion battery pack and the individual lithium-ion battery modules.

[0009] -The entire lithium-ion battery module (including metal, plastic, etc.) is crushed.

[0010] -Magnetic separation / flotation / filtration / extraction of metal and plastic chunks - Washing the powder by a leaching process using inorganic acids.

[0011] - Extracting black mass (e.g. NMC) or separating materials with low reusability or recyclability.

[0012] Dismantling as a pretreatment by mineral acid leaching without further separation processes of the elements: -Discharge the lithium-ion battery pack.

[0013] -Open the lithium-ion battery pack and dismantle the lithium-ion battery module.

[0014] -The lithium-ion module is opened and disassembled down to the lithium-ion battery cells.

[0015] -Opening the lithium-ion battery cells.

[0016] -The electrolyte is removed from the lithium-ion cells by washing them with a liquid.

[0017] -Separate the positive and negative electrodes (active material + current collecting foil).

[0018] -The negative electrode active material is leached with a high pressure inorganic acid stream and the active material is separated from the current collector.

[0019] - Washing the active material.

[0020] -Extract black chunks (e.g. NMC) An example of such an application is disclosed in published patent application CN108285977A, which discloses a method for recycling the cathode material of discarded lithium-ion batteries. The method includes discharging and disassembling the lithium-ion batteries, crushing the lithium-ion batteries to obtain cathode pieces, a leaching process, and a drying process. In this method, the material is crushed, which requires the extraction of different metals before leaching, and the impurities of the material are increased.

[0021] The drawbacks of the recycling process of recovering the active material as black agglomerates and the process steps applied thereto are discussed separately below.

[0022] Shredding By mechanical processing with high forces, pressures and stresses, the feed material is crushed, pulverized and locally incinerated at extreme positions. Furthermore, by applying an inertial medium (to suppress discharges and other undesirable reactions during shredding), the shredding mechanism destroys and incinerates the important raw materials, resulting in high material losses of 20%-40%, resulting in the loss of valuable materials. The recycling efficiency of the "batteries to materials" system can therefore only be less than 80%. This means that one ton of lithium-ion battery (NMC) feed material leads to an economic loss of up to 1,150 euros in current raw material value. Even with conservative calculations, there will be up to 3,000,000 tons of lithium-ion battery recycled material available in 2030, corresponding to an economic loss of up to 3.45 billion euros in material value. Due to the limited raw materials (resources and reserves) used in the production of lithium-ion batteries and the expected exponential increase in the demand for lithium-ion batteries in the coming years, the application of shredders is neither economically nor environmentally profitable and is not wise from a long-term perspective. Moreover, shredding of lithium-ion batteries is not a clean technology that provides reusable products for the lithium-ion battery industry. The powder obtained from a single stage of shredding is often insufficient, and multi-stage shredding is often applied. Furthermore, the powder has high impurity levels, which requires multiple post-processing methods such as flotation, magnetic separation and multi-stage sieving, which increases the number of process steps, complexity, operational costs and reduces the final yield.

[0023] Dismantling and mineral leaching to obtain the black mass. In state-of-the-art methods, the leaching step is combined with a separation step, where a (high pressure) mineral acid stream is applied to separate the anode active material from the current collector. This procedure combines two process steps (separation of active material from the current collector and leaching) into one, which may require less time, but more material is lost as the separated material dissolves in the liquid phase and is subject to strong bombardment and scattering, and additional impurities are introduced due to strong interactions with the metal current collector, resulting in less efficient material recovery. This leaching process is followed by a washing / purification step (often in the form of filtration or sieving), where the dissolved anode active material is collected and dried, resulting in the black mass, which is the accumulation / compound of active material.

[0024] Low quality recovered material / final product or precursor only: Another major drawback of the shredding and separation into black mass or manual dismantling and separation into black mass procedures is that the final product or recovered material is a heterogeneous mixture of materials with unknown properties, purity and various chemical elements, products and compounds. Therefore, the properties of the final black mass are highly dependent on the anode active material fed. Since the chemical composition of the anode active material has different ratios / stoichiometries, obtaining only black masses significantly limits the usefulness of the discharged material, for example, N:M:C=1:1:1 or 8:1:1 or 5:3:2. This means that dismantling or shredding the feed material down to NMC level in the active material recovery / recycling process is only feasible if the same active material chemical composition (ratio) is used to build new anodes. This also limits the use of only one fixed feed material chemical composition. Thus, an ideal recycling process using a battery feed stream based on NMC 1:1:1 active material would produce black mass with approximately NMC 1:1:1 chemical composition, which can be used to manufacture lithium-ion batteries with an anode active material chemical composition of NMC 1:1:1. However, this assumption is only valid if the preceding leaching process is tuned to maximize the leaching capacity of the anode active material, for example by recovering nearly 100% of the feed elements nickel, manganese, cobalt and lithium, when the feed lithium-ion battery NMC is used. Otherwise, the final element ratios will vary and it is not possible to guarantee that the final product will have the desired chemical ratios. In all other cases using mixed feed materials, the final mixture of black mass and anode active materials of various chemical compositions will be of little or no use at all for the manufacture of lithium-ion batteries. Furthermore, recovered black mass is not fully utilized in the production of new lithium-ion battery cells with a 100% recycled / recovered material proportion, currently limited to a 10% proportion in combination with 90% new virgin material, assuming high purity of the recycled material, which is often not achieved.

[0025] Generation of hazardous gases and wastewater due to the use of inorganic acids in the leaching process: The use of inorganic leaching agents to recover lithium-ion battery materials is a factor common to both processes and leads to the generation and emission of hazardous gases and liquids dangerous to humans and nature. This is partly caused by impure pre-treatment and the associated post-treatment to obtain the black mass. Moreover, this leads to further environmental pollution with hazardous substances and may even lead to poisoning of workers. Moreover, the use of hazardous substances requires high active and passive health and safety standards for operators and workers, which are almost impossible to meet in recycling facilities.

[0026] Citric acid is used on shredded material and NMP soaked material Summary of the Invention

[0027] Brief description and objectives of the invention

[0028] The present invention solves the following problems and challenges of the current state-of-the-art solutions for lithium-ion battery recycling (those mentioned in the state-of-the-art section and those not mentioned above):

[0029] -Long waiting / dead time with discharge procedure: State-of-the-art discharge measures use various discharge methods to ensure that the residual voltage remaining in the energy system / lithium-ion battery is less than 0.5V and is a non-safe or dangerous amount. This procedure applies to either lithium-ion battery packs or lithium-ion battery modules. However, since the voltage of lithium-ion batteries recovers after some time and reaches voltage levels up to 40V, lithium-ion battery packs / modules need to be short-circuited after discharge as waiting / dead time of up to 48 hours before further processing. Alternatively, lithium-ion batteries can be discharged with chemical or wet discharge methods using corrosive and aggressive media, which reduces and cuts off the electrochemical potential of the lithium-ion battery. However, this method is very time-consuming and uses inorganic and toxic materials, which leads to pollution and harmful gas emissions, and is mainly applied to lithium-ion battery cells. Moreover, the release of chemicals corrodes the lithium-ion battery from the outside to the inside, reducing the yield and quality of the final material, and introducing further impurities, necessitating a post-processing step for cleaning. Moreover, all currently established state-of-the-art discharge methods are highly limited by the diversity and differences of lithium-ion battery packs, modules and cells, which often only allow them to manage a small portion of this diverse industry, and take a long time to process and plan. However, this invention implements an innovative, automated, and fast discharge route that can handle differently constructed lithium-ion batteries (lithium-ion batteries from different manufacturers, sizes and shapes) at different stages (packs, modules, cells), and overcomes the long waiting / dead time of up to 48 hours by shortening the discharge process time, and does not require additional waiting time. The invention uses an electrical discharge method rather than a wet chemical discharge method.

[0030] High yield losses from shredding: state-of-the-art recycling methods use shredding as a mechanical separation and grinding process to obtain the desired positive active material or valuable materials in lithium-ion batteries, such as lithium, cobalt, nickel, and manganese. Shredding is used to reduce lithium-ion battery modules or packaged materials to particle size to obtain a mixture with up to 40% material loss allowed, and is considered to be a fast and general dismantling method. The present invention maintains the maximum possible rate of packaging material of supplied lithium-ion battery packs, modules, and cells (e.g., cases, cables, plugs, battery management systems) using highly efficient, automated, and parallelizable (modular) dismantling means. However, the main objective of the present invention is to eliminate the use of intense mechanical crushing processes and chemical discharges and rely on a component-by-component separation step to dismantle lithium-ion battery packs into modules, cells, and cell components, resulting in a high quantity and quality of negative active material that is high purity and allows further recycling processing without the need for powder post-processing steps.

[0031] -Other lithium-ion battery materials / components are recovered as powder or shredded parts. State-of-the-art recycling methods either obtain black masses of various chemistries and compositions due to the use of different feed materials, or black masses of a single chemistry if the same lithium-ion battery model is used, or shredding is used. In addition, many materials that are not considered negative active materials, such as electrolytes, separator foils, parts of the metal case, cables, polymers, etc., are lost completely or partially during the shredding process. In currently established shredding-based recycling processes, these materials and parts are deemed unnecessary, worthless, or too complex to be recovered for lithium-ion battery recycling, and at least 20% of the input mass is discarded. The present invention uses a disassembly route as described above, whereby all parts are preserved as far as possible, ideally in their assembled state, whereby these parts do not require further extensive preparatory measures such as methods to filter and sift them from the shredded mass. These other lithium-ion battery parts are rather sorted manually or automatically along the disassembly line into specific material containers, where all similar parts are collected and prepared for further processing or sale without the need for material powder processing. This method therefore increases the overall recycling rate and eliminates the need for remanufacturing lithium-ion battery components, further reducing energy consumption and carbon dioxide emissions.

[0032] -Active materials are often only available as powder accumulations or black agglomerates, limiting the economic sense and efficiency of recycling. State-of-the-art solutions often use mechanical processes such as shredding or other inefficient means to separate or extract the anode active material from the feed material. These methods or processes often only extract a metal powder and a black agglomerate powder mixture as the end product from the recycling process. The economic use of the active material compounds recovered from inside the black agglomerates is limited. Only a limited number of industrial sectors benefit or are interested in the products from these processes, since extensive purification or crystallization processes are required and virgin materials are considered cheaper and easier to introduce into the manufacturing chain. The materials recovered from current processes cannot be used entirely in one product or as reusable materials for the production of lithium-ion batteries. The present invention, as one example, uses a high purity feed anode active material with very low impurities, so no additional washing steps are required and the resulting anode active powder can be chemically processed. Additional post-processing steps are provided, which allow the anode active material to be chemically separated as individual chemical elements in large quantities and with high quality. This primarily contributes to a better, more effective and sustainable pre-processing of lithium-ion batteries (packs, modules and cells) by disassembling them component by component with guaranteed component integrity.

[0033] - Chemical recovery of cathode materials of lithium-ion batteries by inorganic processing: state-of-the-art applications and established methods rely on the use of inorganic substances in various processes. Inorganic agents are used from the beginning to the end of the lithium-ion battery recycling process, as they are highly reactive and often have high performance. However, the inorganic acids used are highly toxic, lead to harmful gases and emissions, cause hazardous wastewater, and require specially trained staff, equipment and storage facilities. For example, acidic processes already start at the time of discharge and are also used in hydrometallurgical processes and in the post-processing steps where the recovered materials are obtained. The highly toxic inorganic acids used are also highly acidic, which requires complex processes. The present invention does not rely on inorganic acids, but replaces many acidic processing steps with alternatives, for example as mentioned above for discharge, and implements alternative, more environmentally friendly acids, such as organic acids. Furthermore, it is also possible to replace the inorganic acids applied in the chemical separation steps with organic acids, which further reduces the toxic health risks for workers. The present application therefore provides a safer and more environmentally friendly recycling process for lithium-ion batteries. Exemplary embodiments of a method for recycling lithium-ion batteries according to the present invention are illustrated in the accompanying drawings. [Brief description of the drawings]

[0034] [Figure 1] 1 is a flow chart of a method for recycling lithium-ion batteries according to an exemplary embodiment of the present invention. [Diagram 2]FIG. 1 is a flow chart of step 5 of a method according to an exemplary embodiment of the present invention. The process in the flow chart is described by vertical lines along the main process steps with capital letters without numbers, and sub-process steps along horizontal lines with capital letters and numbers. Each part in the figure is individually referenced as follows: A Preparing the Li-ion battery, A1 Checking the state of health (SoH), A2 Checking the state of charge (SoC), A3 Discharging the Li-ion battery (pack, module, cell), B Dismantling the Li-ion battery pack, B1 Removing the lid of the Li-ion battery pack, B2 Dismantling and separating the components of the Li-ion battery pack, B2.1 Collecting and obtaining reusable Li-ion battery pack components, B2.2 Collecting and obtaining the Li-ion battery module, C Dismantling the Li-ion battery module, C1 Opening the Li-ion battery module, C2 Dismantling and separating the components of the Li-ion battery module, C2.1 Collecting and obtaining reusable Li-ion battery module components, C2.2 Collecting and obtaining the Li-ion battery cell, D Dismantling the Li-ion battery cell, D1 Opening the Li-ion battery cell, D2 Removing the electrolyte, D3 Dismantling and separating the components of the Li-ion battery cell, D3.1 Collecting and obtaining the separator, D3.2 Collecting and obtaining the positive electrode, D3.3 E Collection and acquisition of negative electrodes, E Removal of binders and residual electrolyte from positive and negative electrodes, E1 Treatment of negative and positive electrodes by heat treatment, E2 Separation of positive and negative active material and current collector foil, E2.1 Collection and acquisition of aluminum foil (negative current collector), E2.2 Collection and acquisition of copper foil (positive current collector), E2.3 Collection and acquisition of positive active material, E2.4 Collection and acquisition of negative active material, E3 Cleaning of acquired positive and negative current collector foils, F Chemical recovery of positive and negative active material, F1.1 Hydrometallurgical treatment of active material with organic acids, F2.1 Recovered positive active material, F2.2 Recovered negative active material, F2.3 Post-processing to obtain positive active material that can be used as a precursor, F2.4 Post-treatment to obtain anode active material that can be used as precursor, G Chemical separation of cathode active material from lithium-ion battery, G1 Separation of cathode active material for binary lithium-ion battery chemistry, G1.1 First separation step of cathode active material, G1.2 Final separation step of cathode active material, G2 Separation of anode active material for ternary lithium-ion battery, G2.1 First separation step of cathode active material, G2.2 Second separation step of cathode active material, G2.3 Third separation step of cathode active material, G2.4 Final separation step of cathode active material, GA.1 Extraction and filtration of first separated cathode active material from lithium-ion battery, GA.2 Extraction and filtration of second separated anode active material from lithium-ion battery, GA.3 Extraction and filtration of third separated anode active material from lithium-ion battery, GA.4 Extraction and filtration of final separated cathode active material from lithium-ion battery, GB.1 GB.2 a post-treatment step of a first separated positive electrode active material from a lithium-ion battery; GB.3 a post-treatment step of a third separated negative electrode active material from a lithium-ion battery; GB.4 post-treatment step of the last separated cathode active material from the lithium-ion battery; H drying and packaging; J1 reuse of the leaching agent; J2 reuse of the extractant in the first anode active material separation process; J3 reuse of the extractant in the second anode active material separation process; J4 reuse of the extractant in the third cathode active material separation process; X1 discharged lithium-ion battery pack; X2 discharged lithium-ion battery module; X3 discharged lithium-ion battery cell; X4 discharged and decomposed cathode and anode; X5 cathode active material; X6 anode active material; X7 recovered cathode active material; X8 recovered and separated individual cathode active material elements; X9 leachate containing anode active material ions from the lithium-ion battery; X10 leachate with one less anode active material ion; X11 leachate with two less anode active material ions; X12 leachate containing only Li-ions; X13 product of the first recovered material from the lithium-ion battery; X14 X15 the second recovered material product from lithium-ion batteries, X16 the last recovered material product from lithium-ion batteries, XP1 the precursor positive electrode material recovered after leaching, XP2 the precursor negative electrode material recovered after leaching. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0035] To overcome the aforementioned challenges in the industry and the shortcomings of state-of-the-art application methods, the following method is proposed and described specifically for lithium-ion battery packs in electric vehicles (EVs), but lithium-ion batteries for other applications such as E-bikes, E-scooters, laptops, mobile phones, or batteries with different structures such as modules and cells can also be recycled in this way. The present invention and process describe a comprehensive approach for recycling raw materials from lithium-ion batteries, including various feed streams of EV packs, modules, and lithium-ion battery cells. Other types of lithium-ion batteries other than lithium-ion battery EV packs can be integrated into the recycling process stream after pretreatment and discharging in the respective process steps depending on the assembly type such as modules (C) and cells (D). Furthermore, the present invention can process all common binary lithium-ion battery chemistries such as LCO, LMO, LNO, and ternary lithium-ion batteries such as NMC and LNMO with different internal stoichiometric compositions, lithium-ion batteries for various applications, and major lithium-ion battery cell types such as cylindrical, pouch, and prismatic cells.

[0036] The present invention relates to a method for recycling lithium-ion batteries, in particular a method based on dry discharge to reuse the discharged energy, dismantling and disassembly as mechanical pretreatment, and organic acid leaching for chemical recovery. The method includes the following steps:

[0037] Step 1: A preparation step (A) including a discharge step (preferably dry discharge) of the diagnostic tool and the lithium-ion battery (A3).

[0038] Step 2: A dismantling, disassembly, separation and collection process of the lithium ion battery, including dismantling the lithium ion battery case, disassembling the lithium ion battery into its components without any crushing or shredding process of the associated materials, and separating and collecting all associated parts down to the components of the lithium ion battery cell such as the negative electrode (positive electrode) with the respective active material composition, the positive electrode (negative electrode) with the respective active material composition, the separator, and the electrolyte, and then collecting other intact and reusable materials implemented in the lithium ion battery system such as the battery pack, case, cables, PMS, PCB (B, C, and D).

[0039] Step 3: Remove the binder between the positive and negative electrodes (E) and individually separate the negative and / or positive active materials from their respective metal current collector foils by thermal, mechanical, or chemical treatments, or any combination of these methods, without introducing impurities or significant degradation, and without removing residual electrolyte.

[0040] Step 4: Chemically recover the anode and cathode active materials (F) separately by environmentally friendly, high-yield hydrometallurgical operations, such as leaching in an organic acid solution (F1) with or without a reducing agent to obtain a leachate in which all target materials (e.g., anode active material metals) of the feedstock are fully or partially dissolved, where chemical recovery of the active materials can be continued to obtain the active material elements individually or chemical precursors of the cathode or anode materials.

[0041] Step 5: The positive and negative active materials in the leachate are chemically separated into their individual chemical elements in a stepwise manner using a reusable agent (G) and processed as individual products.

[0042] Step 6: The final step in the lithium-ion battery recycling process is the cleaning, drying, packaging (H) and preparation process of the materials obtained and separated from the recycling process. The resulting product is prepared for reuse, resale or further processing into a product.

[0043] Step 1 involves preparing the lithium-ion batteries for the discharge process (A) to reduce the risk of thermal runaway, fire, or other potential hazards during processing and to mitigate the potential for charge and threat to the lithium-ion batteries. This step (Step 1) considers lithium-ion battery packs, modules, and cells and includes at least the following preferred discharge procedures:

[0044] The health check (A1) consists of at least one optical and / or electrical and / or mechanical inspection to classify the lithium ion battery and determine its condition for further processing. This process step is important to determine whether the lithium ion battery is healthy or not, its manufacturing type, the technology implemented and to determine the most suitable and most efficient processing route, more precisely the required discharge settings. In a preferred embodiment, with regard to the result of the health check, it is determined whether the lithium ion battery is suitable for recycling or can be used for a secondary use.

[0045] The state-of-charge check (A2) analyzes the state of charge of the Li-ion battery to determine how much electrical energy / residual voltage is still stored / available in the Li-ion battery. This analysis provides the necessary information for parameters regarding the next discharge step, such as the required duration and the applied discharge current.

[0046] Discharging the lithium ion batteries (A3) by electrical means preferably applies a current of 2 to 20 amperes and a duration of 1 to 120 minutes to discharge the lithium ion batteries. The amount of current and the discharge time within the given limits are determined depending on the determined remaining amount of electrical energy stored in the lithium ion batteries with reference to the previous step. The lithium ion batteries are preferably discharged below 2 volts, which is the critical voltage level for processing, and most preferably to a voltage level of about 0.5 V per lithium ion battery module. If the lithium ion batteries are not discharged to a voltage below the critical integrity voltage level (about 0.5 V), handling the lithium ion batteries is very dangerous since further processing involves the risk of thermal runaway, short circuit and fire. In a preferred embodiment, the discharge energy obtained in step 1 is used directly to power subsequent steps of the recycling process, reintroduced into the grid, used to charge other applications of the lithium ion batteries (e.g. second life applications) or used for other applications (such as EV charging stations), so that the discharged energy is not lost.

[0047] The entire step 1 (A), or at least the lithium-ion battery discharging step (A3), may be partially or fully automated. Furthermore, lithium-ion batteries entering the recycling process as lithium-ion battery packs require special pre-treatment. The lithium-ion battery packs must be opened and the lithium-ion battery modules removed from the lithium-ion battery packs in order to discharge all lithium-ion battery modules in the lithium-ion battery packs to ensure a safe process and to bypass the BMS of the battery pack while maintaining the structural integrity of the lithium-ion batteries. Opening the lithium-ion battery packs may be done manually or automatically by removing joints, fasteners, screws or cutting the case. The appropriate method is determined from the preparation step (step 1) of the health check (A1).

[0048] After step 1, the discharged lithium-ion batteries (pack: X1, module: X2, cell: X3) will be subjected to the respective dismantling process steps (pack: B, module: C, cell: D) shown in step 2 above.

[0049] The overall step 2 of the EV lithium-ion battery pack preferably includes the following sub-steps:

[0050] The lithium-ion battery pack is disassembled down to the lithium-ion battery modules (B) which are then collected and retrieved together with other reusable lithium-ion battery pack components.

[0051] The lithium-ion battery module is disassembled down to the lithium-ion battery cells (C), which are then collected and obtained together with other reusable lithium-ion battery module components.

[0052] Dismantle and disassemble a lithium-ion battery cell down to its components (D), such as anode, cathode, separator, and electrolyte, with minimal impact to the integrity, high yield, and purity rate of the cell's components.

[0053] In the disassembly process, which will be described in more detail below, the lithium-ion batteries are disassembled primarily by mechanical means, but the process may be supported by thermal and / or optical systems, and by thermal, thermo-mechanical, chemical, thermo-chemical, or mechano-chemical means.

[0054] -To dismantle and disassemble the lithium-ion battery pack (B) down to the lithium-ion battery modules, i.e. to preserve the recyclable and valuable lithium-ion battery pack components such as aluminum, steel, copper, cables, electronics, plastics, etc., the lithium-ion battery pack needs to be dismantled and disassembled manually or automatically. This procedure includes:

[0055] Once the lithium-ion battery pack case is opened, the lid is manually or automatically removed and retrieved to expose the lithium-ion battery pack interior and components (B1).

[0056] - Dismantle and separate the components (B2) of the lithium-ion battery pack, which can be done manually or automatically o Further classification into recyclable or reusable lithium-ion battery pack components (B2.1), e.g., copper, aluminum, cables, plastics, mixed metals, and other parts other than the modules, which are further classified, processed, and prepared for reuse in other applications (e.g., reprocessing) or for sale.

[0057] o Lithium-ion battery module (B2.2): The discharged lithium-ion battery module (X2) is transported (manually or automatically) to the next recycling process step (C) after its internal voltage is checked again and the non-critical voltage is verified based on the possible voltage relaxation effect. The lithium-ion battery module is the component that needs to be further disassembled and processed to reach the lithium-ion battery cell where the valuable materials are implemented.

[0058] Dismantle and disassemble the lithium-ion battery module (C) down to the lithium-ion battery cells. To further save valuable recyclable components, the lithium-ion battery module needs to be dismantled manually or automatically. Furthermore, it is necessary to reach the lithium-ion battery cells and cell components without damaging, degrading or contaminating them, as these are the most valuable materials in a lithium-ion battery. This procedure includes:

[0059] -Open the lithium-ion battery module (C1) manually or automatically.

[0060] - Lithium-ion battery module component (C2) can be manually or automatically o Further recyclable or reusable components (C2.1), e.g. copper, aluminum, cables, plastics, mixed metals, etc., which can be further sorted and processed; and o Disassemble and separate the lithium-ion battery cells (C2.2) which can have one of three different shapes / structures: pouch-shaped, prismatic, or cylindrical. The discharged lithium-ion battery cells (X3) are transported manually or automatically to the next recycling process step (D). The lithium-ion battery cells are the components that need to be further disassembled and processed to obtain the cathode, anode, and other components that contain valuable materials.

[0061] Dismantling a lithium-ion battery cell (D) into lithium-ion battery cell components such as anodes, cathodes, separators, and electrolytes. Manual or automated dismantling and disassembly of lithium-ion battery cells is necessary to preserve valuable components and materials in large quantities and at high quality, and to minimize the processing steps required. By utilizing process steps such as dismantling and disassembly rather than relying on shredding, process steps such as magnetic separation, sieving, and flotation separation can be eliminated. Furthermore, if the quality and purity of the feed materials such as cathodes and anodes are obtained at the highest possible purity levels through dismantling and dismantling, higher yields and purity will be achieved in subsequent chemical processing. This procedure includes:

[0062] -Manually or automatically opening lithium-ion battery cells (D1) in a protected, sealed environment to prevent the release of dangerous gases and as a safety measure against other threats.

[0063] - If the lithium-ion battery cell is opened and the separator foil is removed prior to thermal measures, e.g., heated in a vacuum oven or furnace under high temperature inert gas environment for a period of time, the electrolyte (D2) is extracted or removed by flushing the open cell with liquid, using supercritical fluids, using CO2 gas, or by thermal means. Extraction and removal of the electrolyte is necessary for further processing of the positive and negative active materials based on the liquid state of the electrolyte, which interferes with the subsequent separation process. The electrolyte does not necessarily need to be obtained or recovered, but it needs to be removed before further processing.

[0064] -Disassembly and separation of components of lithium-ion battery cells (D3): When the non-thermal pretreatment of (D2) is used, the internal components and case of the lithium-ion battery cell are separated during extraction of the electrolyte, and the parts / products are separated and classified into the following:

[0065] o Separators (D3.1): Separators are plastic components in lithium-ion battery cells that prevent short circuits during the charging and discharging process. After separation, the separators are collected for further processing.

[0066] o Positive Electrode (D3.2): The positive electrode is the negative current collector of a lithium-ion battery cell and receives lithium ions from the negative electrode during the charging process. The main components of the positive electrode are the current collector foil (usually copper), the binder (usually PVFD), and the active material (usually a graphite composition, or a silicon composition). The positive electrode is subjected to the next process step to remove the binder that binds the current collector foil and the active material.

[0067] o Anode (D3.3): The anode is the positive current collector of a lithium-ion battery cell, which transports lithium ions to the cathode during the charging process. The main components of the anode are the current collector foil (usually aluminum), the binder (usually PVFD), and the active material (various compositions of Ni, Mn, Co, Fe, P, Li, or in this case essentially LCO, LNO, LMO, NMC). The anode is subjected to the next process step to remove the binder that binds the current collector foil and the active material.

[0068] - Preferably, the discharged and decomposed positive and negative electrodes (X4) are transported (manually or automatically) to the next main process step (E).

[0069] Step-by-step dismantling and disassembly of lithium-ion batteries, either manually or automatically, as described above, is necessary to preserve valuable components and active materials (both anodes and cathodes) that are subject to the recycling process and need to be recovered so that they can be reused, further increasing the efficiency and effectiveness of recycling. Furthermore, dismantling and disassembly are necessary to obtain the best material input and quality of cell components such as cathodes, anodes and other components. To increase the purity of the final recovered elements, it is necessary to separate the components of the lithium-ion battery cell (separator, electrolyte, cathode, anode) to arrive at a process stream with the cathode and anode active materials separated.

[0070] In step 3, the binder between the positive and negative electrodes is removed (E), and the active materials of the negative and / or positive electrodes are separated from the respective metal current collector foils, and the active materials are further recovered by a chemical organic leaching process. In addition to removing the binder, the residual electrolyte in the respective positive and negative electrodes is also removed. This step preferably includes the following sub-steps:

[0071] -Heat Treatment (E1): Thermal dissolution at high temperatures is important to 1) remove the binder, 2) increase the surface area of ​​the valuable active material elements, and 3) remove residual electrolyte. The binder can be dissolved / evaporated by a thermal treatment such as pyrolysis by heating the positive and negative electrode compositions in a vacuum or inert gas environment furnace to temperatures between 250°C and 650°C and holding these temperatures for 10 to 120 minutes at a temperature increase rate (heating rate) of 5 to 15°C per minute, with a nitrogen gas flow if necessary.

[0072] -Separation of active material and current collector (E2): After removal of the binder, the positive and negative electrodes are processed to separate the active material from the corresponding metal current collector. This separation can be done mechanically, chemically, gravitationally, or by a combination of these. For example, separation can be achieved by scraping or shaking the active material off the current collector (mechanical process) or by rinsing the active material in a water bath or stream (chemical process) followed by drying. After separation of the positive and negative active materials from their respective current collectors, the components are classified into parts / products as follows:

[0073] o Aluminum foil from the negative electrode current collector (E2.1), o Copper foil from the positive current collector (E2.2), o the active material of the positive electrode (E2.3) consisting of a graphite or silicon composition, o A negative electrode active material (E2.4) consisting of a combination of chemical elements such as, but not limited to, nickel, manganese, cobalt, and lithium.

[0074] - Cleaning process of the obtained positive and negative current collector foils (E3): The separated current collector foils need to be cleaned to increase their material value before packaging and sale. This can be done by washing with distilled / deionized water under or without ultrasonic assisted means. In this step, aluminum and copper foils are processed.

[0075] Preferably, the resulting positive active material (X5) and negative active material (X6) are transported manually or automatically to the next process step (F) and treated separately.

[0076] Manual or automated separation of the active material of lithium-ion battery cells from the current collector foils is necessary to preserve valuable components and active materials in large quantities and in high quality without the need for additional process steps, allowing the separated active material to be introduced directly into the respective processing stream.

[0077] In step 4, chemical recovery of the positive and negative active materials (F) is performed. Chemical organic recovery of the active materials is achieved by dissolving the obtained solid mass of active materials in a reusable leachate (J1) from which the individual substances can be recovered, thus increasing the value of the materials recovered from the recycling process as reusable materials. Chemical recovery of the positive electrode (graphite, silicon, etc.) and negative electrode materials (based on nickel, cobalt, manganese, lithium compositions, etc.) is carried out in separate reactors, in physically separated processes that are independent of each other and not combined, where negative electrode materials with similar chemical properties such as NMC and LCO can be mixed. Chemical recovery preferably consists of the following operations:

[0078] - Hydrometallurgical processing using organic acids such as citric acid, malic acid, and / or formic acid (F1.1) as leaching agents: Leaching the active material with organic acids improves the environmental impact and process efficiency. It increases the recycling efficiency and reduces toxicity while at the same time generating less harmful gases. The concentration of the leaching agent in the leaching solution is preferably set to 0.5M-3.0M, and the leaching process is carried out at a temperature of 60.1°C-99.9°C for 15-120 minutes. The solid-to-liquid ratio is set to 10-120g / L. This organic leaching process can be used with or without organic or inorganic reducing agents to increase the recovery efficiency, discharge rate, and treatment performance. The reducing agent includes at least one of hydrogen peroxide, sodium thiosulfate, sodium bisulfite, D-glucose, sucrose, or ascorbic acid, and is added to the leaching solution at a concentration of 0.1-10% by volume. As a result of this process, the following materials are obtained:

[0079] o The cathode active material recovered from the cathode leaching process (F2.1): This is a composition of graphite or silicon or a mixture of graphite and silicon, which can be processed into precursors (F2.3) and conveyed manually or automatically to a drying and packaging step (H) to obtain the final cathode active material product, e.g. a graphite or silicon or a mixture of graphite and silicon product (XP1).

[0080] o Anode active material recovered from the anode leaching process (F2.2): This consists of a composition of different anode active material elements that can be processed into precursors that can be considered as final reusable products (F2.4), extracted from the process chain and transported manually or automatically to a drying and packaging step (H), resulting in a precursor material with a fixed stoichiometric composition (XP2), which can be further used for the manufacture of new lithium-ion battery cells, with the restriction of using the same composition ratio / stoichiometric composition. However, to improve usability, the recovered cathode active material (F2.2) is preferably further processed in a separation process (G). In this case, the recovered cathode active material (X7) is preferably transported to the next process (G).

[0081] The chemical recovery process can be applied to lithium-ion batteries from one source or application, but also to mixed lithium-ion battery streams from different applications and chemistries such as NMC-111, NMC-811, NMC-532, or chemistries that depend on elements present in NMC chemistries such as LCO, LNO, and LMO batteries.

[0082] After step 4, the recovered / leached anode active material (X7) is transported manually or automatically to the next process step (step 5) to separate the recovered anode active material composition into its chemical elements, improving reusability and flexibility of the process discharge material. Thus, after step 4, the next step 5 is performed on the recovered anode active material.

[0083] Step 5: Chemical separation of the positive active material from the lithium-ion battery (G) is carried out by a procedure of sequential chemical separation of the target material from the leachate containing metal ions such as lithium, nickel, cobalt, manganese, etc. in any order (the exemplary embodiment shown in FIG. 2 is not fixed in the separation order but only distinguishes between two-component and three-component recycling, which includes additional extraction process steps). This includes:

[0084] - Sequential separation of individual metals from the leachate to obtain a carrier solution containing the target metal ions (binary systems: G1.1 and G1.4 only, otherwise G2.1 to G2.4).

[0085] -Transfer of the target metal from the first carrier / extraction solution to the second carrier solution (binary systems only: GA.1 and GA.4, otherwise GA.1-GA.4) and obtain the previously applied agents (J2, J3, J4) necessary to create the first carrier / extraction solution, which allows the agents to be recovered and reintegrated into the chemical extraction process (in G).

[0086] - Obtaining the target metal from the second carrier solution and separating the resulting solidified / precipitated metal material from the second carrier solution by a filtration process (for binary systems only: GB.1 and GB.4, or GB.1-GB.4).

[0087] In a preferred embodiment, chemical separation of the negative electrode active material components includes the following.

[0088] - Sequential separation of individual metals from the leachate to obtain a first carrier solution containing only one target metal ion type.

[0089] - Separating the first carrier solution from the residual leachate.

[0090] -Transferring the target metal from the extracted first carrier solution to a second carrier solution and obtaining the previously applied extractant for reuse.

[0091] - Obtaining the target metal as a solid residue from the second carrier solution by precipitation and filtration.

[0092] In another preferred embodiment, the chemical separation of the negative electrode active material elements includes:

[0093] - Sequential separation of metals individually from the leachate to obtain a solid residue containing only one target metal ion type in the solid residue compound.

[0094] - Filtering the solid residue from the residual leachate.

[0095] - The target metal is transferred from the solidified residue to a carrier solution, obtaining previously used extractant for reuse.

[0096] - Precipitation and filtration obtains the target metal from the carrier solution as a solid residue.

[0097] As shown in FIG. 2, in a preferred embodiment of the present invention, step 5, which is chemical separation of the negative electrode active material element (G), includes:

[0098] - Isolating cathode active materials for binary lithium-ion battery chemistries (G1): This isolation process is for anode active material compositions based on lithium and other transition metals (cobalt, manganese, nickel, etc.).

[0099] o First separation step of the negative active material (G1.1): Separation of the transition metals from the leachate.

[0100] o Final separation step of the negative active material (G1.2): Extraction of lithium from the residual leachate.

[0101] - Isolating anode active materials for ternary lithium-ion battery chemistries (G2): This isolation process is for anode active material compositions based on combinations of lithium and transition metals such as cobalt, nickel, and manganese.

[0102] o First separation step of the negative active material (G2.1): Separation of one transition metal from the leachate.

[0103] o Second separation step of the negative active material (G2.2): Separation of the other transition metals from the leachate.

[0104] o Third separation step of the negative active material (G2.3): Separation of the other transition metals from the leachate.

[0105] o A third separation step of the negative active material (G2.3); separating the other transition metals from the leachate.

[0106] As shown in FIG. 2, an exemplary leachate containing ternary lithium-ion battery chemistry including nickel, cobalt, manganese, and lithium ions (X9) is obtained from the anode active material chemical recovery (F2.2) step, with the separation of the first transition metal resulting in the remaining leachate (X10) containing one less transition metal species, the second separated leachate (X11) containing two less transition metal species, and the final unseparated leachate (X12) containing only or mainly lithium ions.

[0107] In step 5, the chemical separation process of the valuable metals (positive active material elements) from the leachate (G) is divided into separation steps for each chemical element contained in the leachate. Separation can be performed by direct precipitation from the leachate into a solidified compound and / or by solvent extraction (liquid-liquid extraction) in any order. In a preferred embodiment, after filtration and separation of one component from the leachate, the former solution is divided into a carrier solution or precipitate and a residual leachate, which are further used in the next process step to separate the remaining chemical elements from the leachate.

[0108] The following extractants, in conjunction with the phase stabilizer tributyl phosphate (TBP) and dilute kerosene (at varying concentrations and volume contents), can be used to separate precious metals from the leachate:

[0109] Chemical extractants, diluents and solvents for liquid-liquid extraction: -Cyanex272, -D2EHPA, -PC88A, -Versatic 10 Neodecanoic Acid, -Trioctylphosphine oxide (TOPO), -benzoyltrifluoroacetone (HBTA), - Trioctylamine (TOA).

[0110] The chemical precipitation extractant does not require kerosene as a phase stabilizer or diluent.

[0111] Chemical extractants for precipitation: -Dimethylglyoxime (DMG), -Sodium phosphate, sodium sulfate, sodium hydroxide, sodium carbonate, -Ammonium oxalate.

[0112] In a preferred embodiment, step 5 comprises at least one of the active material processes "Isolate the active cathode material of a binary lithium-ion battery chemistry" (G1) or "Isolate the active cathode material of a ternary lithium-ion battery chemistry" (G2) shown below, including the following substeps and details:

[0113] Separating the negative active material of binary lithium-ion battery chemicals (G1): Taking LCO (LiCoO2) as an example, the transition metal cobalt is first extracted from the leachate, followed by the extraction of lithium. However, by choosing different optimized process conditions, the reverse process is also possible, where lithium is extracted first, then cobalt, and finally lithium. The separation step involves the recovery of metal ions from the leachate into an organic phase by chemical reaction or direct precipitation, and the resulting solution or compound containing the extracted metal ions is separated from the remaining leachate solution containing the remaining transition metals. The separated solution or compound containing the recovered metal ions is further processed in extraction and filtration steps, where the target metal is transferred to a separate phase and the agent initially used for the solvent extraction process is recovered. The recovered metal ions are precipitated, filtered, and obtained as a compound that can be further processed in post-treatment steps. The above process can also be applied to other binary lithium-ion battery chemicals, such as LNO and LMO, in which case the separation process of the respective transition metals can be obtained from the process of ternary lithium-ion batteries described below. In particular, recovery of the LCO cathode active material from the leachate includes the following:

[0114] -Selectively separate the cobalt from the leach solution (G1.1) by precipitation or solvent extraction. Depending on the method chosen, other reagents / extractants are available. For example, ammonium oxalate (0.1-2 mol / L) selectively precipitates cobalt oxalate hydrate (CoC2O4·2H2O). Optimal process conditions in a reactor with constant stirring and heating are temperatures between 15-30 °C and pH levels between 4-7. Chemical reaction times are 20-90 min. Alternatively, separate the cobalt from the leach solution by solvent extraction (GA.1). For this, chemical extractants such as Cyanex 272, PC-88A, and / or Cyanex 272 with tributyl phosphate (TBP) can be used to selectively extract the cobalt. This chemical reaction occurs between pH 3-6.5. Either the resulting cobalt oxalate hydrate or the organic solution containing the extracted metal in ionized form is then separated by filtration or other means from the residual leachate (GA.1) containing other metal ions. The separated medium carrying the first extracted anode active material (solid or liquid) is then treated with an acid such as sulfuric acid and then with sodium carbonate or sodium sulfate as part of a post-treatment (GB.1).

[0115] - Lithium is selectively separated from the leach solution (G1.2) preferably by precipitation, but can also be treated by solvent extraction. Saturated sodium carbonate is used as chemical reagent at a temperature of about 100 °C, pH = 11-13 for 20-60 minutes, ideally with a lithium ion to sodium carbonate molar ratio of 0.2-1.5. Another chemical reagent for separating lithium from the leach solution is sodium phosphate at 0.2-2 mol / L. Lithium can be extracted by DEHPA at 0.06 mol L-1, organic to aqueous ratio (O / A) = 1:1, pH = 2-4. Alternatively, lithium is extracted from the leachate under the conditions of pH=7-9, 0.4 mol L-1 HBTA+0.4 mol L-1 TOPO+kerosene, O / A=1:1, 70% saponification, and extraction for 2 min, and then the lithium-containing solution (GA.4) is separated from the residual leachate by filtration and treated with sodium carbonate in post-treatment (GB.4).

[0116] The cathode active material of the ternary lithium-ion battery chemistry (G2) is separated, where the separation order of the transition metals nickel, cobalt, and manganese is variable. Thus, the following separation order is possible:

[0117] [Table 1] Lithium is often extracted last, but there are extraction conditions where lithium can be extracted first and then extracted again as the final extraction step. The following description describes the process for separating ternary lithium-ion batteries in the separation order of cobalt, nickel, manganese, and lithium. The methods described here for each individual material can also be used for other orders. The separation step involves the recovery of metal ions from the leachate into an organic phase by chemical reaction or direct precipitation, whereby the resulting solution or compound containing the extracted metal ions is separated from the remaining leachate solution carrying the remaining transition metals, and then further processed to separate the other metal ions. The separated solution or compound containing the recovered metal ions is further processed in extraction and filtration steps to transfer the target metal to a separate phase and recover the agent originally used for the solvent extraction process. The recovered metal ions are precipitated, filtered, and obtained as a compound that can be further processed in post-treatment steps. The above process can be applied to mixtures of binary and ternary lithium-ion battery chemistries, or to ternary lithium-ion batteries only. In detail, the recovery of the negative electrode active material from the leachate of at least a ternary lithium ion battery includes the following:

[0118] The steps of separation or direct precipitation of the transition metals in an organic phase (G2.1, G2.2, G2.3, G2.4), extraction and filtration steps of the solution or compound containing the separated metal ions (GA.1, GA.2, GA.3, GA.4) transfer the metals of interest to a separate phase and recover the reagents initially used for the solvent extraction process. The extracted metal ions are then obtained as compounds by post-treatment steps (GB.1, GB.2, GB.3, GB.4). The following procedure is illustratively described for NMC's ternary lithium-ion battery chemicals and an exemplary separation sequence for cobalt, nickel, manganese, and lithium.

[0119] -Cobalt is selectively separated from the leach solution (G2.1) by precipitation or solvent extraction. Depending on the method chosen, other reagents / extractants are available. For example, ammonium oxalate (0.1-2 mol / L) selectively precipitates cobalt oxalate hydrate (CoC2O4·2H2O). Optimal process conditions in a reactor with constant stirring and heating are temperatures between 15-30 °C and pH levels between 4-7. Chemical reaction times are between 20-90 min. Alternatively, cobalt is separated from the leach solution by solvent extraction (GA.1). For this, chemical extractants such as Cyanex 272, PC-88A, and / or Cyanex 272 with tributyl phosphate (TBP) can be used to selectively extract cobalt. This chemical reaction occurs between pH 3-6.5. Either the resulting cobalt oxalate hydrate or the organic solution containing the extracted metal in ionized form is then separated by filtration or other means from the residual leachate (GA.1) containing other metal ions. The separated medium carrying the first extracted anode active material (solid or liquid) is then treated with an acid such as sulfuric acid and then with sodium carbonate or sodium sulfate as part of a post-treatment (GB.1).

[0120] - Nickel is selectively separated from the leachate / leachate by adding reagents / extractants (G2.2). Nickel is extracted by dimethylglyoxime (DMG) at a concentration of 0.02-0.2 mol / L, at a temperature range of 15-30°C, at a pH range of 4-5 or 7.4-10, for 5-60 minutes, and after a chemical reaction, the nickel ion solution is extracted and filtered (GA.2), and nickel products are obtained by post-treatment (GB.2). Post-treatment (GB.2) includes treatment with hydrochloric or sulfuric acid at 3 mol / L-5 mol / L. Nickel is then selectively separated by ammonium hydroxide at 1-3 mol / L, or sodium carbonate or sodium sulfate at a pH range of 2.5-5.

[0121] - Manganese is selectively separated from the leachate by precipitation or solvent extraction (G2.3). Manganese ions are separated from the leachate by using chemical reagents such as di-(2-ethylhexyl) phosphoric acid (D2EHPA) or sulfonated kerosene (GA.3). D2EHPA is saponified 60-85% with concentrated sodium hydroxide (5-13 mol / L). Additionally, 1-8 vol% tributyl phosphate is used. The manganese-bearing organic phase is separated from the leachate (GA.3) and filtered, where the applied extractant is recovered. The resulting manganese-containing solution is treated with an inorganic acid solution, such as sulfuric acid, and then with sodium carbonate or sodium sulfate as part of a post-treatment step (GB.3).

[0122] - Lithium is selectively separated from the leach solution (G2.4) preferably by precipitation, but can also be treated by solvent extraction. To directly treat the lithium ion-containing leach solution (GB.4), saturated sodium carbonate is used as the chemical reagent at a temperature of about 100 °C, pH = 11-13 for 20-60 minutes, ideally with a molar ratio of lithium ions to sodium carbonate of 0.2-1.5. Another chemical reagent for separating lithium from the leach solution is sodium phosphate at 0.2-2 mol / L. Lithium can be extracted by DEHPA at 0.06 mol L-1, organic to aqueous solution ratio (O / A) = 1:1, pH = 2-4. Alternatively, lithium is extracted from the leachate under the conditions of pH=7-9, 0.4 mol L-1 HBTA+0.4 mol L-1 TOPO+kerosene, O / A=1:1, 70% saponification, and extraction for 2 min, and then the lithium-containing solution (GA.4) is filtered to separate it from the residual leachate and treated with sodium carbonate in the post-treatment (GB.4).

[0123] The separated and extracted positive electrode active materials (X13, X14, X15, X16) from each separation step obtained after post-treatment (GB.1, GB.2, GB.3, GB.4) are transferred by manual or automatic means to the next processing step, i.e., step 6, drying and packaging step (H).

[0124] Following step 5, in the drying and packaging step (H), the final processing is carried out, whereby the drying process of the separated active material elements (X13, X14, X15, X16) and / or the obtained precursor materials (XP1, XP2) is carried out. The drying process is preferably carried out in a closed facility, for example in a vacuum oven or in an inert gas oven, to suppress oxidation and agglomeration, which is connected with a step of automatic or manual packaging of the final product / element in an airtight bag. In a preferred embodiment, the drying time is set to 0.5-8.0 hours, and the drying temperature is set to 50°C-250°C, preferably 70°C. The drying environment is preferably carried out under normal atmospheric pressure and an inert gas atmosphere such as argon or nitrogen.

Claims

1. A method for recycling lithium ion batteries, comprising the steps of: a preparation step comprising diagnosing the lithium ion battery followed by opening the lithium ion battery pack and discharging the lithium ion modules and / or cells; A dismantling and disassembly process for a lithium ion battery, comprising dismantling a case of the lithium ion battery, disassembling the lithium ion battery into cell components to obtain a negative electrode having a respective active material composition, a positive electrode having a respective active material composition, a separator, and an electrolyte, and collecting other components implemented in the energy system of the lithium ion battery; - removing the binder between the positive and negative foils and the respective active material compositions, and separating the positive and negative current collector foils individually from the respective active materials; a process for separately chemically recovering the separated anode and cathode active materials by hydrometallurgical operations; and - A method for recycling lithium-ion batteries, characterized by a process for the individual and subsequent chemical separation of the negative electrode active material down to its individual chemical elements and processing as individual products.

2. 2. The method for recycling a lithium ion battery according to claim 1, wherein the initial preparation step comprises: - checking the health status to determine whether the lithium-ion batteries are suitable for recycling, identifying their production type and shape, and preparing the digital data sets necessary for the subsequent discharge process; - checking the state of charge to determine the amount of electrical energy / residual voltage still stored in the Li-ion battery and to determine the process parameters required for the next discharge step; - discharging the lithium ion battery module by electrical means using a discharge current and duration based on data obtained from the health / charge check.

3. 3. The method for recycling lithium ion batteries according to claim 1 or 2, comprising the steps of: - dismantling and disassembling the lithium-ion battery pack into lithium-ion battery modules and recovering reusable parts to obtain the lithium-ion battery modules; a sub-step of dismantling the lithium ion battery module into lithium ion battery cells, collecting reusable parts, and obtaining the lithium ion battery cells; and a sub-step of dismantling the lithium-ion battery cell into its components and obtaining the components of the lithium-ion battery cell, such as anodes, cathodes, separators, and electrolytes.

4. 4. The method of recycling lithium ion batteries of claim 3, wherein the lithium ion batteries are disassembled and disassembled by at least one of mechanical, thermal, thermomechanical, chemical, thermochemical, or mechanochemical means, or any other combination of these methods.

5. A method for recycling lithium ion batteries according to any one of the preceding claims, comprising the steps of: - heat treatment to remove binders and residual electrolytes; - Separating the positive and negative active materials from the current collector foils; - classifying the components into current collector foil, positive electrode active material, and negative electrode active material.

6. 5. A method for recycling a lithium-ion battery according to claim 1, wherein the chemical recovery of the positive and negative active materials is carried out in separate, physically separated processes and the active materials are not recombined.

7. 2. A method for recycling lithium-ion batteries as claimed in any one of the preceding claims, wherein the hydrometallurgical operation comprises individually leaching the active materials in an organic acid solution to obtain a leachate containing all of the target metals of the respective positive or negative electrode active material feed composition.

8. 8. A method for recycling lithium ion batteries as claimed in claim 7, wherein the leaching is carried out using an organic acid solution comprising at least one of citric acid, formic acid and / or malic acid.

9. 9. A method for recycling lithium ion batteries as claimed in claim 7 or 8, wherein the hydrometallurgical or organic leaching process involves an organic or inorganic reducing agent.

10. 10. The method of recycling a lithium ion battery according to claim 9, wherein the reducing agent comprises at least one of hydrogen peroxide, sodium thiosulfate, sodium bisulfite, D-glucose, sucrose, or ascorbic acid.

11. 11. A method for recycling a lithium-ion battery according to claim 7, wherein the chemical separation of the negative or positive active material comprises separate chemical separation of the negative or positive active material from the leachate.

12. 12. The method for recycling lithium-ion batteries according to claim 11, wherein the chemical separation of the negative electrode active material elements is performed by sequential chemical separation / extraction of the target metals from the leachate in any order using at least one of the metal ions of lithium, nickel, cobalt, and / or manganese by solvent extraction or direct precipitation.

13. 13. The method for recycling a lithium ion battery according to claim 11 or 12, wherein the chemical separation of the negative electrode active material elements comprises the steps of: - sequentially separating metals individually from said leachate to obtain a carrier solution containing only one target metal ion type or to obtain a residue carrying the metal ions using direct precipitation methods; - separating the carrier solution or the residue from the leachate; - transferring the target metal from the extracted carrier solution or residue to another solution, allowing the previously used extractant to be reused; - obtaining the target metal as a solid residue from the solution by precipitation and filtration.

14. A method for recycling lithium-ion batteries according to any one of claims 11 to 13, wherein after filtering and separating one substance from the leachate, the former solution is divided into a precipitate and a residual leachate which are further used in a next process step to separate the remaining components.

15. A method for recycling lithium ion batteries according to any one of the preceding claims, wherein the lithium ion batteries are any of lithium ion battery assemblies such as packs or modules for different applications, and / or lithium ion battery cells of any of the following cell types: cylindrical, pouch or prismatic cells.

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