Classifications

• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B1/00—Preliminary treatment of ores or scrap
  • C22B1/005—Preliminary treatment of scrap
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/54—Reclaiming serviceable parts of waste accumulators
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B1/00—Preliminary treatment of ores or scrap
  • C22B1/02—Roasting processes
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B23/00—Obtaining nickel or cobalt
  • C22B23/04—Obtaining nickel or cobalt by wet processes
  • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
  • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
  • C22B26/10—Obtaining alkali metals
  • C22B26/12—Obtaining lithium
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
  • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
  • C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
  • C22B3/1608—Leaching with acyclic or carbocyclic agents
  • C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
  • C22B3/165—Leaching with acyclic or carbocyclic agents of a single type with organic acids
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
  • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
  • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
  • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
  • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B47/00—Obtaining manganese
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
  • C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
  • C22B7/006—Wet processes
  • C22B7/007—Wet processes by acid leaching
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/84—Recycling of batteries or fuel cells

Definitions

• the present invention is related to the recycling of Lithium-Ion Batteries; especially from applications of E-Mobility like electric vehicles but not limited to these and offers a highly efficient recycling method for Lithium-Ion Batteries achieving high recovery rates by effective pretreatment and hydrometallurgical procedures.
• LiBs Lithium-Ion Batteries
• LiBs are considered as exceptionally reliable and efficient technology for sustainable and green (electric) energy storage systems due to several reasons like high energy densities and power per unit of battery weight, allowing them to be lighter and smaller than other rechargeable batteries.
• New research and manufacturing methods for Lithium-Ion Batteries are providing increased storage capacities, faster charging speeds, and longer overall lifespans.
• new developments and innovations in this sector strongly rely on the availability and price of virgin raw materials that are mined in non-European and nonMediterranean countries and primarily by foreign entities.
• the state-of-the-art Lithium-Ion Battery recycling considers the recycling of Lithium-Ion Battery cathode active materials like compositions of Lithium- Nickel- Manganese- Cobalt - Oxide (NMC), Lithium- Cobalt - Oxide (LCO), Lithium-Manganese -Oxide (LMO) or Lithium- Nickel - Oxide (LNO) whereas other important components of a Lithium-Ion Battery pack are either unconsidered, badly recovered or destroyed.
• NMC Lithium- Nickel- Manganese- Cobalt - Oxide
• LCO Lithium- Cobalt - Oxide
• LMO Lithium-Manganese -Oxide
• LNO Lithium- Nickel - Oxide
• the recovery of the Lithium-Ion Battery materials can be done by recovering cathode materials compositions as a combination of products and compounds of the cathode active elements Nickel, Cobalt, Manganese, and Lithium with varying stoichiometry.
• This powder mixture of active material compounds with varying contents of chemical elements is an accumulation and often referred to as “black mass” wherein impurities of iron, phosphor, aluminum, copper, and plastics can still be present. It is important to emphasize that the initial cathode active materials, e.g.
• Nickel-Manganese-Cobalt, Lithium-Cobalt-Oxide, or Lithium- Ferrous-Phosphate (LFP) are not recycled and recovered as separate chemical pure elements but as collective chemical products/ compounds with some degree of impurities as precursor materials.
• Some recycling procedures recover elements but are only capable of reaching recycling efficiencies below 80% (under optimistic assumption) when the input material mass is considered to the output material mass (input mass vs. recovered mass of output materials).
• Anode materials and other implemented materials, e.g. metallic collectors are also recovered however mostly in form of mixed and crushed powders which are recovered with a high impurity level and require additional purification steps.
• the core process of current recycling methods resolves around “shredding/ crushing” as a mechanical pretreatment process in order to reduce the volume and gain a maximum of up to 75% of the mass of active materials implemented in Lithium-Ion Batteries by crushing Lithium- Ion Batteries into small-sized pieces.
• Lithium-Ion Battery modules (with casings, plastics, adhesives, connectors, battery cells, etc.) are reduced by shredding down to micrometer particle size before separating the dissimilar materials of the received powder mixture, e.g. into the active materials of cathode, anode, and collector materials.
• Leaching cathode active material with high-pressure inorganic acids stream to separate active material from collector
• the application discloses a method for recycling waste Lithium-Ion Battery positive electrode materials.
• the method comprises the steps of discharging the Lithium-Ion battery, disassembling it, and crushing the Lithium-Ion battery to obtain the positive electrode piece, a leaching process, and a drying process.
• the materials are crushed, whereby different metals need to be extracted before leaching which increases the impurity of the materials.
• Shredding Due to the mechanical procedure with high forces, pressures and stresses the input materials are crushed, milled, and in local extreme positions incinerated. Additionally, by applying an inertia medium (to suppress electrical discharges during shredding, or other undesired reactions), the shredding mechanism leads to the destruction and incineration of critical raw materials yielding high material losses between 20% to 40%, whereby valuable materials are lost. Therefore, the recycling efficiency of the system “battery to material” only has an efficiency of lower than 80%. This means, that 1 ton Lithium-Ion Battery (NMC) input material relates to an economic loss of up to 1’150 € in terms of current raw material values.
• NMC Lithium-Ion Battery
• the leaching step is combined with the separation step where the cathode active material is separated from the collector by applying (high-pressure) inorganic acid streams. While this procedure might require less time due to the combination of 2 process steps in one (active material separation from collector and leaching), more material is lost due to the strong impact and scatter of separated materials dissolved in the liquid phase, additional impurities are introduced due to the strong interactions with the metallic collector, whereby no efficient material recovery is present.
• a cleaning/ purification step is required after this leaching process (often in form of filtration or sieving), where the dissolved cathode active material is collected and dried, whereby the black mass, an accumulation/ compound of the active materials, is obtained.
• the recovered black mass cannot be completely utilized for building new Lithium- Ion battery cells with a share of recycled/ recovered materials of 100% but is limited down to a share of currently 10% in combination with 90% new virgin materials, assuming a high purity of the recycled materials, which is often not achieved.
• the present invention solves the following problems and challenges of the current state-of-the- art solutions for recycling Lithium-Ion Batteries (for the ones given in the state-of-the-art section and others that were not mentioned above):
• the state-of-the-art discharging measures use different discharging methods to ensure a safe or not dangerous amount of residue voltage left in the energy system/ Lithium-Ion Battery of lower than 0.5 V whereby this procedure is laid out for either Lithium-Ion Battery pack or Lithium-Ion Battery module.
• the voltage of the Lithium-Ion Battery experiences a voltage recovery after some time and reaches voltage levels of up to 40 V whereby the Lithium-Ion Battery pack/ module needs to be short-circuited after discharging for up to 48 hours as waiting/ dead time before processing it further.
• the Lithium-Ion Batteries can be discharged in chemical or wet discharging methods by using corrosive and aggressive media, whereby the electrochemical potential of the Lithium-Ion Batteries is reduced and cut off.
• this method is very slow, uses inorganic and toxic agents, leads to pollution and hazardous gas emissions and is mainly applicable for Lithium-Ion Battery cells.
• the chemical discharging corrodes the Lithium-Ion Batteries from the outside to the inside, leads to decreased final material yields and qualities, introduces further impurities, and requires posttreatment steps for the cleaning.
• the state-of-the-art recycling methods use shredding as mechanical separation and grinding process to obtain the desired cathode active materials or valuable materials inside the Lithium-Ion Batteries, like Lithium, Cobalt, Nickel, Manganese.
• Shredding is used and considered a fast and common dismantle method to get the Lithium-Ion Battery modules or implemented materials down to particle size and obtain a mixture whereby a material loss of up to 40% is accepted.
• the present invention will use high-efficient, automated, and parallelizable (modular) disassembling measures to preserve the maximum possible rate of implemented materials of the input Lithium-Ion Battery packs, modules, and cells (e.g. case, cables, plugs, battery management system, etc.).
• the main objective of the invention is the achievable high quantity and quality of cathode active materials by discarding the use of strong mechanical crushing processes as well as chemical discharging and relying on part-by-part separation steps, that include the dismantling of Lithium-Ion Battery packs to modules to cells to cell components whereby high purity materials are obtained for further recycling processing without the need for powder posttreatment steps.
• Lithium-Ion Battery materials/ parts are recovered as powders or shredded parts: the state-of-the-art recycling methods use shredding to obtain black mass of varying chemistry and compositions due to the use of different input materials or black mass of single chemistry when the same Lithium-Ion Battery models are being used. Additionally, many materials are either completely or partly lost during the shredding process that are not considered cathode active materials, like the electrolyte, separator foil, parts of metallic casings, cables, polymers and more. The current established recycling processes that are based on shredding deem these materials and parts unnecessary, not worth, or too complex to recover for recycling Lithium- Ion Batteries and discard them with a total of at least 20% of the input mass.
• the present invention will use a disassembling route as describe above, whereby all parts will be preserved as much as possible and ideally as they were implemented whereby these parts do not require any further extensive preparation measures like methods to filter and sieve them from shredded masses.
• These other Lithium-Ion Battery parts will rather be sorted manually or automatically along the disassembly line into specific material containers where all similar parts will be collected and then prepared for further processing/ or sales without the need for material powder processing. This method therefore has an increased overall recycling share, further reduces the energy consumption and carbon gas emission by eliminating the need for the reproduction of Lithium-Ion Battery parts.
• Active materials are often only available as one powder accumulation or black mass limiting the economic significance and efficiency of recycling:
• the state-of-the-art solutions often use mechanical processes like shredding as well as inefficient measures to separate or extract the cathode active materials from the input materials.
• These methods or processes often only extract metal powders and black mass powder mixtures as final products from the recycling process.
• the recovered active material compounds inside the black mass have limited economical applications. Limited industrial sectors would benefit or be interested in the products from these processes since extensive purification or crystallization processes are needed whereby virgin materials are considered cheaper and easier to implement into the manufacturing chain.
• the recovered materials from current processes cannot be fully used in one product or as re-usable materials for the Lithium-Ion Battery production.
• the present invention for one uses highly pure input cathode active materials with exceptionally low impurities whereby no additional cleaning step is required, and the obtained cathode active powders can be chemically processed. Additional post-processing steps are provided that enable the chemical separation of the cathode active materials as individual chemical elements in high quantities and qualities which is mainly attributed to the more suitable, effective, and sustainable pretreatment of Lithium-Ion Batteries (packs, modules, calls) by disassembly them part-by-part wherein the part integrities are warranted.
• the present invention does not rely on inorganic acids but replaces many acidic process steps with alternatives, e.g. as described above for the discharging, and implements alternative and more environmentally friendly acids like organic acids. Additionally, the applied inorganic acids for chemical separation steps can also be replaced by organic acids which further decrease the toxic health risks for operators. Therefore, the present application provides a safer and environmentally friendlier recycling process for Lithium-Ion Batteries.
• FIG. 1 Flowchart of the Lithium-Ion Battery recycling method with respect to an exemplary embodiment of the invention.
• FIG. 2 Flowchart of the step 5 of the method with respect to an exemplary embodiment of the invention.
• the process in the flowchart is described by vertical lines along the main process steps with capital letters without numbering and subprocess steps along the horizontal lines with capital letters and numbering.
• the parts in said figures are individually referenced as following.
• SoC State of Charge
• the following method is proposed and described especially for Lithium-Ion Battery packs of electrical vehicles (EVs), whereas other Lithium-Ion Batteries of other applications such as E-Bikes, E-Scooters, Notebooks, Mobile phones, etc. or from different builds, e.g. modules and cells, can be recycled by this method as well.
• the invention and process describe a comprehensive approach for the recycling of raw materials from Lithium-Ion Batteries including various input streams for EV packs, modules, and Lithium-Ion Battery cells.
• Lithium-Ion Batteries except Lithium-Ion Battery EV packs can be integrated into the recycling process stream after the pretreatment and discharging in their respective process steps according to their built type, e.g. modules (C) or cells (D). Additionally, the invention can process all common binary Lithium-Ion Battery chemistries like LCO, LMO, LNO and ternary Lithium-Ion Batteries like NMC and LNMO with different internal stoichiometric compositions, Lithium-Ion Batteries of different applications and all major Lithium-Ion Battery cell types like cylindrical, pouch and prismatic cells.
• the present invention relates to a recycling method of Lithium-ion Batteries, especially based on dry discharging wherein the discharged energy is reused, dismantling and disassembling as mechanical pretreatment and organic acid leaching for the chemical recovery.
• the method comprises the following steps:
• Step 1 Preparation step (A) which comprises a diagnostic tool and discharging step (preferably dry discharging) of Lithium-Ion Batteries (A3).
• Step 2 Dismantling, disassembling, separating, and collecting processes for Lithium-Ion Batteries which comprises dismantling the Lithium-Ion Battery casings, disassembling the Lithium-Ion Batteries part-by-part without any crushing or shredding process for any materials involved and thus separating and collecting all relevant parts down to the Lithium-Ion Battery cell components like cathode (positive electrode) with its respective active material composition, anode (negative electrode) with its respective active material composition, separator, and electrolyte; next to the collection of other undamaged and reusable materials that are implemented in the Lithium-Ion Batteries system e.g. battery pack, casing, cables, PMS, PCB’s (B, C and D).
• Step 3 Removal of the binding agent between anode and cathode (E) to separate the active materials of the cathode and/or anode from their respective metallic collector foils individually by either thermal, mechanical, or chemical treatments or by any combination of these methods without introducing any impurities or strong deteriorations and removing any residual electrolyte.
• Step 4 Chemical recovery of active materials (F) of cathodes and anodes separately with environmentally friendly hydrometallurgical operations with high yield rates, such as leaching in organic acid solutions (Fl) with or without reducing agents to obtain a leaching liquor with all target materials of the input material (e.g. cathode active material metals) dissolved completely or partly; wherein the chemical recovery of active materials is continuable to obtain either the active material elements individually or obtain a chemical precursor agent of anode or cathode materials.
• active materials (F) of cathodes and anodes separately with environmentally friendly hydrometallurgical operations with high yield rates, such as leaching in organic acid solutions (Fl) with or without reducing agents to obtain a leaching liquor with all target materials of the input material (e.g. cathode active material metals) dissolved completely or partly; wherein the chemical recovery of active materials is continuable to obtain either the active material elements individually or obtain a chemical precursor agent of anode or cathode materials.
• Step 5 Chemical separation and processing of cathode and anode active materials inside the leaching liquor separately down to their individual chemical elements as individual products by stepwise methods with reusable agents (G).
• Step 6 Cleaning, drying, packaging (H) and preparation processes of the obtained and separated materials from the recycling process as finishing steps of the recycling process for Lithium-Ion Batteries.
• the obtained products after the final steps are prepared for re-use, re-sale, or further processing as products.
• step 1 preparation of Lithium-Ion Batteries for the discharging process (A) is performed, in order to reduce the risk of thermal runaway, fire or other possible danger potentials during processing; thus, disarming the charge and threat potential of the Lithium-Ion Batteries.
• This step (step 1) considers Lithium-Ion Battery packs, modules and cells and at least comprises the following preferably discharging procedure:
• State of Health check (Al); which comprises at least one of optical and/ or electrical and/ or mechanical examination, in order to classify the Lithium-Ion Batteries and determine their status for further processing.
• This process step is important to determine whether the Lithium- Ion Battery is healthy, to determine its built type, its implemented technology, and therefore determine the most suited and most efficient processing route, or more precise, the required discharging setup.
• it is determined whether the Lithium-Ion Battery is suitable for recycling or whether it can be used for a second life usage.
• state of charge check (A2); where the state of charge of the Lithium-Ion Battery is analyzed in order to determine the rest amount of electrical energy / residual voltage still stored/ available in the Lithium-Ion Battery.
• This analysis gives the necessary information for the parameters about the following discharging step; like required duration and discharge current to be applied.
• Discharging the Lithium-Ion batteries (A3) by electrical means wherein preferably currents of 2 to 20 Ampere and a duration of 1 to 120 minutes are applied in order to discharge the Lithium- Ion Battery. The amount of current and discharging duration within the given limits is determined with reference to the previous step; according to the determined rest amount of electrical energy stored in the Lithium-Ion Battery.
• the Lithium-Ion Battery is preferably discharged under the critical voltage level for processing of 2 Volts and most preferably to a voltage level of about 0.5 V for every Lithium-Ion Battery module. Without discharging the Lithium-Ion Battery lower than the critical integrity voltage level (which is about 0.5 V), the treatment of the Lithium-Ion Battery would be too dangerous based on carrying the risk of thermal runaways, short circuits and inflaming when further processed.
• the discharging energy that is obtainable in step 1 will be either directly used to power the recycling processes further steps, re-introduced to the grid, used to charge other applications of Lithium-Ion Batteries (e.g. second life applications) or used for other applications (like EV charging stations) whereby the discharged energy will not be lost.
• the whole step 1 (A) or at least discharging the Lithium-Ion Battery step (A3) is partly or fully automated. Furthermore, a special pre-process is needed for Lithium-Ion Batteries that are introduced to the recycling process as Lithium-Ion Battery packs.
• the Lithium-Ion Battery packs need to be opened whereby the Lithium-Ion Battery modules need to be disconnected from the Lithium-Ion Battery pack in order to discharge every single Lithium-Ion Battery module of the Lithium-Ion Battery pack to guarantee a safe process, and to bypass the BMS of the battery pack while keeping the structural integrity of Lithium-Ion Batteries intact. Opening the Lithium-Ion Battery pack can be performed manually or automatically by releasing the joints, closures, screws and/ or cutting the enclosing case.
• the suitable method will be determined from the preparation step (step 1) during the State of Health check (Al).
• Step 1 the discharged Lithium-Ion Battery (pack: XI, module: X2, cell: X3) is manually or automatically transferred to the respective dismantling process step (pack: B, module: C, cell: D) given above as Step 2.
• the whole step 2 for an EV Lithium-Ion Battery pack preferably comprises the following substeps: Dismantling and disassembling the Lithium-Ion Battery pack down to Lithium-Ion Battery modules (B) which are collected and obtained next to other reusable Lithium-Ion Battery pack components;
• D Lithium-Ion Battery cell components
• Lithium-Ion Batteries are disassembled primarily by mechanical means, but the process can be supported by thermal and/ or optical systems and like thermal, thermomechanical, chemical, thermochemical, or mechano-chemical means
• Dismantling and disassembling the Lithium-Ion Battery pack (B) down to Lithium-Ion Battery modules the manual or automated dismantling and disassembling of the Lithium-Ion Battery pack is necessary in order to save recyclable and valuable Lithium-Ion Battery pack components like aluminum, steel, copper, cables, electronics, plastics, etc. This procedure comprises:
• Lithium-Ion Battery pack components which comprises sorting the components manually or automatically into o further recyclable or re-usable Lithium-Ion Battery pack components (B2.1): e.g., Copper, Aluminum, Cables, Plastic, mixed metals, and other parts than the modules that are further sorted, processed, and prepared for re-use in other applications (e.g. as re-furbishing) or for sale.
• Lithium-Ion Battery modules (B2.2) the discharged Lithium-Ion Battery modules (X2) are checked for their internal voltage again and transported (manually or automatically) to the next recycling process step (C) after validating the non-critical voltage based on possible voltage relaxation effects.
• Lithium-Ion Battery modules are the components that need to be further disassembled and processed in order to reach the Lithium-Ion Battery cells in which the valuable materials are implemented. Dismantling and disassembling the Lithium-Ion Battery modules (C) down to the Lithium-Ion Battery cells: the manual or automated disassembling of the Lithium-Ion Battery module is necessary to save further recyclable and valuable components. Furthermore, it is necessary to reach the Lithium-Ion Battery cells and cell component materials without damaging, deteriorating, or contaminating them as these are the most valuable materials of the Lithium- Ion Battery. This procedure comprises:
• Lithium-Ion Battery module components C2 manually or automatically into o Further recyclable or re-usable components (C2.1): e.g., Copper, Aluminum, Cables, Plastic, mixed metals, etc. that are further sorted and processed and; o Lithium-Ion Battery cells (C2.2) that can have one of three different shapes/ builds: pouch, prismatic, cylindric.
• the discharged Lithium-Ion Battery cells (X3) are transported manually or automatically to the next recycling process step (D).
• Lithium-Ion Battery cells are the components that need to be further disassembled and processed in order to obtain the anode, cathode, and further components in which the valuable materials are.
• the manual or automated dismantling and disassembling of the Lithium-Ion Battery cell is necessary in order to save valuable components and materials at high quantities and qualities and to minimize required treatment steps.
• process steps like dismantling and disassembling and not relying on shredding process steps like magnetic separation, sieving and floatation can be discarded.
• the following chemical processing will achieve higher yields and pureness if the quality and pureness of the input materials like anode and cathode are obtained at the highest purity level possible which is possible with dismantling and disassembling.
• This procedure comprises:
• Lithium-Ion Battery cells either manually or automatically in a protected and closed surrounding to prevent the release of hazardous gas emissions and as a safety precaution against other threats.
• o Separator the separator is a plastic component in the Lithium-Ion Battery cell that avoids short circuits during the charge and discharge process. After the separation, separators can be collected and further processed.
• o Anode the anode is the negative collector of the Lithium-Ion Battery cell and receives Lithium-ions from the cathode during a charging process.
• the main components of the anode are a collector foil (usually copper) a binding agent (usually PVFD) and the active material (usually graphite composition, or alternatively silicon composition).
• the anode is taken to the next process step in order to remove the binding agent that is connecting the collector foil and the active material; and o Cathode (D3.3):
• the cathode is the positive collector of the Lithium-Ion Battery cell and sends Lithium-ions to the anode during a charging process.
• the main components of the cathode are a collector foil (usually aluminum), a binding agent (usually PVFD) and the active material (different compositions of Ni, Mn, Co, Fe, P, Li, or as in our case basically LCO, LNO, LMO, NMC).
• the cathode is taken to the next process step in order to remove the binding agent that is connecting the collector foil and the active material.
• the manual or automated dismantling and disassembling of the Lithium-Ion Batteries step by step as given above is necessary to save valuable components and active materials (of cathodes and anodes alike) that are targeted by the recycling process and need to be recovered in order to be able to reuse them, and further increase the recycling efficiency and effectiveness. Furthermore, dismantling and disassembling are necessary to obtain the highest material input quantity and quality of the cell components like the anode, cathode, and further components.
• the separation of the Lithium-Ion Battery cell components is necessary to reach a separated process stream for anode and cathode active materials in order to increase the purity of the final recovered elements.
• step 3 the binding agent between the anode and cathode is removed (E) to separate the active materials of the cathode and/or anode from their respective metallic collector foils in order to further recover the active materials in the chemical organic leaching process. Besides the removal of the binding agent also some residual electrolytes inside the respective anodes and cathodes will be removed as well.
• This step preferably comprises the following sub-steps:
• the thermal dissolvement with elevated temperatures is important in order to 1) remove the binding agent and 2) to increase the surface of valuable active material elements and 3) remove any residual electrolyte.
• the binding agent can be dissolved/ evaporated with a thermal procedure like pyrolysis by heating the anode and cathode composition in a vacuum or inert gas environment furnace up to a temperature between 250°C and 650°C and holding these temperatures for durations of 10 to 120 minutes with a temperature increase rate (heating rate) of 5 to 15 °C per minute wherein if necessary, a nitrogen gas stream is used.
• the components are sorted into the parts/ products as follows: o Aluminum foil (E2.1) from cathode collector, o Copper foil (E2.2) from anode collector, o Active material of anode (E2.3) consisting of a graphite or silicon composition, o Active material of cathode (E2.4), e.g., consisting of chemical element combinations like Nickel, Manganese, Cobalt, and Lithium but not limited to these chemical elements;
• the separated collector foils need to be cleaned to improve the material value before packaging and selling. This can be performed by washing them in distilled/ deionized water under ultrasonic-assisted measures or without.
• the aluminum foil and the copper foils are processed in this step.
• the obtained active material of anode (X5) and active material of the cathode (X6) are transported manually or automatically, to the next process step (F) and are processed separately.
• step 4 chemical recovery of active materials of cathode and anode (F) is provided.
• the chemical organic recovery of the active materials is achieved by dissolving the obtained solid mass of active materials in a reusable leach liquor (JI) from which the individual materials can be recovered, thus improving the value of recovered materials from the recycling process as reusable materials.
• the chemical recovery of the anode (graphite, silicon or other) and cathode materials e.g., based on compositions of Nickel, Cobalt, Manganese, Lithium
• the chemical recovery consists preferably of the following operations:
• - Hydrometallurgical processing with organic acid (Fl.l) like citric acid, malic acid, and/or formic acid as leaching agents Leaching the active materials with organic acids improves the environmental impact and process efficiency. It generates less hazardous gases while it increases the recycling efficiency and has a lower toxicity.
• the concentration of the leaching agents within the leaching solution is preferably set from 0.5 M to 3.0 M.
• the leaching process is conducted at temperatures from 60.1 °C to 99.9°C for a duration between 15 to 120 minutes.
• the solid to liquid ratio is set to be between 10 - 120 g/L.
• This organic leaching process can be accompanied with or without organic or inorganic reduction agents to increase the recovery efficiency, output rate, and processing performance.
• the reduction agent comprises at least one of hydrogen peroxide, sodium thiosulfate, sodium bisulfite, D-glucose, sucrose, or ascorbic acid and is added to the leaching solution with a concentration of 0.1 to 10 vol%. Resulting from this process, the following materials are obtained: o Recovered active material of anode (F2.1) from anode leaching process, which is a composition of graphite or silicon or mixed graphite and silicon and can be processed to a precursor (F2.3) which can manually or automatically be transferred to the drying and packaging step (H) where the final anode active material product is obtained, e.g. graphite or silicon or mixed graphite and silicon products (XP1).
• F2.1 o Recovered active material of anode
• anode leaching process which is a composition of graphite or silicon or mixed graphite and silicon and can be processed to a precursor (F2.3) which can manually or automatically be transferred to the drying and packaging step (H) where the final anode active material
• o Recovered cathode active material (F2.2) from cathode leaching process which consists of compositions of different cathode active material elements that can be processed to a precursor which can be considered as a final re-usable product (F2.4), extracted from the process chain and manually or automatically transferred to the drying and packaging step (H) where the precursor material with a fixed stoichiometric composition (XP2) is obtained and can be further used in new Lithium-Ion Battery cell productions with the limitation of using the same composition ratio/ stoichiometric composition.
• the recovered cathode active material (F2.2) is further processed in the separation process (G).
• the recovered cathode active material (X7) is transferred to the next process (G).
• the chemical recovery process is applicable for Lithium-Ion Batteries from one source or application whereas it is also applicable for mixed Lithium-Ion Battery streams from different applications and chemistries, like NMC-111, NMC-811, NMC-532, etc. or chemistries that rely on elements that are present in the NMC chemistry, like LCO, LNO, LMO batteries.
• step 4 the recovered/ leached cathode active materials (X7) can be transported manually or automatically to a next process step; step 5; to separate the recovered cathode active material composition into its chemical elements to increase the re-usability and flexibility of the process output materials. Therefore, after step 4 the following step 5 is performed for the recovered cathode active material:
• Step 5 Chemical separation of cathode active materials from Lithium-Ion Batteries (G) is performed by sequential chemical separation procedures of target materials from the pregnant leach liquor with metal ions like Lithium, Nickel, Cobalt and/or Manganese, in arbitrary order (the exemplary embodiment given in Figure 2 is not fixed to a separation order but differentiates the recycling of solely binary and ternary systems wherein additional extraction process steps are included), which comprises the following:
• chemical separation of cathode active material elements comprises the following:
• the chemical separation of cathode active material elements comprises:
• step 5 which is the chemical separation of cathode active material elements (G) comprises the following:
• Separation of cathode active materials of binary Lithium-Ion Battery chemistries (Gl): This separation process is for cathode active material composition based on Lithium and another transition metal (e.g., Cobalt or Manganese or Nickel).
• o First separation step of cathode active material (Gl .1); to separate the transition metal from the leach liquor.
• o Last separation step of cathode active material G1.2; to extract the Lithium from the residual leach liquor.
• Separation of cathode active materials of ternary Lithium-Ion Battery chemistries (G2): This separation process is for cathode active material composition based on Lithium and combinations of transition metals like Cobalt, Nickel and/ or Manganese.
• an exemplary leach liquor comprising a ternary Lithium-Ion Battery chemistry with Nickel, Cobalt, Manganese, and Lithium ions (X9) is coming from chemical recovery of cathode active material (F2.2) step; and with the separation of first transition metal, the remaining leach liquor (XI 0) carries one less type of transition metal; the leach liquor after the second separation (XI 1) carries two less transition metals and the leach liquor before the last separation (XI 2) only or mainly carries Lithium ions.
• step 5 the chemical separation process of valuable metals (cathode active material elements) from the leaching liquor (G) is divided into separation steps for each chemical element present in the pregnant leach liquor.
• the separation can be done via direct precipitation from the leach liquor into a solidifying compound and/ or by solvent extraction (liquid-liquid extraction) in arbitrary orders.
• the former solution is divided into a carrier solution or precipitate and residual leach liquor, which will be further used in the next process step to separate the remaining chemical elements from the leach liquor.
• TOPO Trioctylphosphine oxide
• HBTA Benzoyltrifluoroacetone
• step 5 comprises at least one of the “Separation of cathode active materials of binary Lithium-Ion Battery chemistries” (Gl) or “Separation of cathode active materials of ternary Lithium-Ion Battery chemistry” (G2) active materials processes given below with the following sub-steps and details:
• the separation step includes the recovery of metal ions from the leach liquor into an organic phase by chemical reaction or direct precipitation, whereby the resulting solution or compound with the extracted metal ion is separated from the remaining leaching solution which carries the remaining transition metals and is processed further to separate the other metal ions.
• the separated solution or compound with the recovered metal ions is further treated in the extraction and filtration step to transfer the target metal into another phase and recover the initially used agent for the solvent extraction process.
• the recovered metal ions are then precipitated, filtered, and obtained as a compound which can be further processed in posttreatment steps.
• the above-mentioned process can be laid out also for other binary Lithium-Ion Battery chemistries like LNO and LMO wherein the separation process for the respective transition metal can be taken from the below described process for ternary Lithium-Ion Batteries.
• the recovery of the cathode active materials of LCO from leach liquor comprises:
• Cobalt is selectively separated from the leaching solution (Gl.l) via precipitation or solvent extraction.
• other reagents/ extractants can be utilized.
• ammonium oxalate (0.1-2 mol/L) selectively precipitates cobalt oxalate hydrate (CoC2O4-2H2O).
• the optimal process conditions in a reactor under constant stirring and heating are given by: temperature between 15 - 30°C, at pH levels between 4 - 7.
• the chemical reaction time is between 20 - 90 min long.
• Cobalt is separated from the leaching solution through solvent extraction (GA.l).
• a chemical extractant like Cyanex272, PC-88A and/or Cyanex272 with tributyl phosphate (TBP) can be used to extract Cobalt selectively.
• This chemical reaction takes place between 3 - 6.5 pH.
• either the obtained cobalt oxalate hydrate or organic solution which contains the extracted metal in ionized form are separated from the residue leach liquor (GA.l) which contains the other metal ions by filtration or other means.
• the separated medium that carries the first extracted cathode active material (either as solid or liquid) is treated with acids like sulfuric acid and afterwards with sodium carbonate or sodium sulfate as part of the posttreatment (GB.l).
• Lithium is selectively separated from the leaching solution (G1.2) preferably by precipitation but can also be processed by solvent extraction.
• Another chemical reagent to separate Lithium from leaching liquor is sodium phosphate with 0.2 - 2 mol/L.
• the Lithium carrying solution (GA.4) is then filtered and separated from the residual leach liquor and treated with sodium carbonate in the posttreatment (GB.4).
• Cobalt Nickel Manganese Whereas Lithium is frequently extracted at last but there are also extraction conditions whereby Lithium can be extracted first and then again as the last extraction step.
• the separation step includes the recovery of metal ions from the leach liquor into an organic phase by chemical reaction or direct precipitation, whereby the resulting solution or compound with the extracted metal ion is separated from the remaining leaching solution which carries the remaining transition metals and is processed further to separate the other metal ions subsequentially.
• the separated solution or compound with the recovered metal ions is further treated in the extraction and filtration step to transfer the target metal into another phase and recover the initially used agent for the solvent extraction process.
• the recovered metal ions are then precipitated, filtered, and obtained as a compound which can be further processed in posttreatment steps.
• the above-mentioned process can be laid out for mixtures of binary and ternary Lithium-Ion Battery chemistries or for solely ternary Lithium-Ion Batteries.
• the recovery of the cathode active materials from leach liquor of at least ternary Lithium-Ion Batteries comprises:
• Cobalt is selectively separated from the leaching solution (G2.1) via precipitation or solvent extraction.
• other reagents/ extractants can be utilized.
• ammonium oxalate (0.1-2 mol/L) selectively precipitates cobalt oxalate hydrate (CoC2O4-2H2O).
• the optimal process conditions in a reactor under constant stirring and heating are given by: temperature between 15 - 30°C, at pH levels between 4 - 7.
• the chemical reaction time is between 20 - 90 min long.
• Cobalt is separated from the leaching solution through solvent extraction (GA.l).
• a chemical extractant like Cyanex272, PC-88A and/or Cyanex272 with tributyl phosphate (TBP) can be used to extract Cobalt selectively.
• This chemical reaction takes place between 3 - 6.5 pH.
• either the obtained cobalt oxalate hydrate or organic solution which contains the extracted metal in ionized form are separated from the residue leach liquor (GA.l) which contains the other metal ions by filtration or other means.
• the separated medium that carries the first extracted cathode active material (either as solid or liquid) is treated with acids like sulfuric acid and afterwards with sodium carbonate or sodium sulfate as part of the posttreatment (GB.l).
• Nickel is selectively separated (G2.2) from the leaching solution/ leach liquor by adding a reagent/ extractant.
• Nickel is extracted by Dimethylglyoxime (DMG) at concentrations between 0.02 - 0.2 mol/L, in a temperature range of 15 - 30°C, and pH range between 4 - 5 or 7.4 to 10 for a duration of 5 min to 60 min.
• DMG Dimethylglyoxime
• the Nickel ion solution gets extracted and filtrated (GA.2) whereby Nickel products are obtained by post-treatments (GB.2).
• the post-treatment includes the treatment with hydrochloric acid between 3 mol/L - 5 mol/L or sulfuric acid.
• Nickel is selectively separated with ammonium hydroxide between 1 - 3 mol/L under a pH range between 2.5 - 5 or by sodium carbonate or sodium sulfate.
• Manganese is selectively separated (G2.3) from the leaching solution via precipitation or solvent extraction.
• chemical reagents like Di-(2-ethylhexyl) phosphoric (D2EHPA) acid and sulfonated kerosene
• D2EHPA Di-(2-ethylhexyl) phosphoric
• kerosene a complex metal hydroxide
• tributyl phosphate with 1 - 8 vol% is used.
• the Manganese-loaded organic phase is separated and filtered from the leach liquor (GA.3) whereby the applied extraction agent is recovered.
• the obtained Manganese carrying solution is treated with inorganic acid solutions like sulfuric acid and then treated with sodium carbonate or sodium sulfate as part of the posttreatment steps (GB.3).
• Lithium is selectively separated from the leaching solution (G2.4) preferably by precipitation but can also be processed by solvent extraction.
• the Lithium carrying solution (GA.4) is then filtered and separated from the residual leach liquor and treated with sodium carbonate in the posttreatment (GB.4).
• the separated and extracted cathode active materials (X13, X14, X15, X16) from the respective separation steps that are obtained after the posttreatment are transferred to the next processing step, namely step 6, the drying and packaging step (H) either manually or by automated means.
• the drying and packaging step (H) the final processing is conducted; wherein the drying process of the separated active material elements (X13, X14, X15, X16) and/ or obtained precursor materials (XP1, XP2) is conducted.
• the drying process is preferably performed in a hermetical facility to suppress oxidation and agglomeration, e.g. inside a vacuum furnace or inert gas furnace, whereby an automated or manual packaging of the final products/ elements into air-tight bags is connected.
• the drying duration is set to a period of 0.5 to 8.0 hours
• the drying temperature is set between 50°C to 250°C and preferably to 70°C.
• the drying environment is under an inert gas like argon or nitrogen at normal atmospheric pressure.

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