Battery recirculation method

Abstract

The invention is a new route for recycling batteries used in the field of electrical and electronic equipment as well as in the field of automobiles. The present invention encompasses square, cylindrical, and pouch type cells having different types of active cathode materials, such as LCO (), NCA (), LMO (or), NMC (), and LMO-NMC (-). The method comprises the steps of discharging the battery, detaching and separating battery components, grinding the battery cells, precipitating fluorine and lithium, leaching with an acid, separating manganese by ozonation, precipitating aluminum, extracting cobalt by solvent, precipitating nickel and precipitating the remaining lithium. The invention includes an acid leaching step without the use of a reducing agent, which can achieve values near 99% efficiency for Ni, Co, Mn and Li, as well as machining without any heat treatment to concentrate the metal of interest in the battery cathode. The invention also relates to a lithium ion battery recycling method using a metal separation route by ozonation followed by electrodialysis, and a lithium ion battery recycling method using a metal separation route by electrodialysis.

Description

TECHNICAL FIELD

[0001] The present invention relates to a battery recycling process in the field of electronics and automotive. More particularly, the present invention relates to a hydrometallurgical process for recycling lithium-ion batteries in pouch, cylindrical and prismatic (or called prismatic) form having different cathode types such as LCO ( ), NCA ( ), LMO ( or ), NMC ( ) and LMO-NMC ( – ). BACKGROUND

[0002] Lithium-ion batteries (LIBs) are widely used in portable electronic devices and electric vehicles as they can provide high energy and power per unit battery weight. However, the growing demand for raw materials that make up these batteries can not be easily met, particularly in countries where the availability of such resources is limited. Moreover, improper disposal of spent LIBs can lead to serious environmental and safety issues. Currently, the recovery of lithium and cobalt from primary and spent LIBs has become a key issue for the industry producing or consuming LIBs, as these metals are classified as critical raw materials by the European Union and as critical and strategic minerals by the United States, Brazil, Australia and Canada. Therefore, the recycling of spent LIBs is highly relevant from both environmental and economic perspectives. Thus, LIB recycling can reduce the dependence on mining of mineral resources, especially scarce cobalt and nickel, and also contributes to the concept of circular economy and sustainable development. Therefore, the recycling of LIBs has attracted wide attention in recent years.

[0003] Generally, there are two main routes for the recycling of LIBs. The first route combines pyrometallurgy with subsequent hydrometallurgy, while the second route combines mechanical processing (usually after thermal pretreatment) with metallurgical processing. Both routes have a series of advantages and disadvantages in terms of human health, safety and environment, potential recovery rate of components, technical process requirements and economic factors. The recycling methods are usually focused on a single type of battery and include a thermal processing step. Lithium is recovered in only a few types of methods and with relatively low yield. The recovery of low-value components such as graphite and manganese is technically feasible but economically challenging.

[0004] A typical hydrometallurgical process consists of thermal pretreatment, acid or alkaline leaching, separation, purification and product recovery. Acid leaching is the most critical step, where solid-liquid extraction occurs and metals are transferred to the aqueous phase.

[0005] The document US20210395859 relates to the leaching of NMC battery active materials using sulfuric acid and sodium thiosulfate. It mentions the use of a reducing agent to leach the metals directly from the active material without the need for prior physical processing. The document WO2022006469 uses sulfur dioxide gas as a reducing agent to leach the metals with sulfuric acid (at a higher concentration than the method proposed in this patent). The document US20220136079A1 reports the use of citric acid and organic waste (fruit juice) as reducing agents. Xuan et al. (2021) evaluated the use of HC1 as a leaching agent for the active material of NMC batteries without the need for physical processing (grinding and sieving) of the batteries. However, while Xuan et al. (2021) did not use a reducing agent in the method, the gases released when using HC1 are toxic and polluting, unlike sulfuric acid.

[0006] In addition, regarding the processing of the batteries to be recycled in the existing methods, a brine solution is usually used to cause short circuits in the batteries, thus allowing subsequent grinding without explosion. Alternatively, inert gases such as , and argon) can be used in the grinding stage.

[0007] Therefore, there is a gap in the development of a lithium battery recycling method that is applicable to different types of batteries (particularly soft pack, cylindrical and prismatic), which is more environmentally friendly, cost-effective and technically feasible. SUMMARY

[0008] Object of the invention

[0009] In this regard, the present invention aims to provide a battery recycling method, more particularly, for lithium ion batteries in soft pack, cylindrical and prismatic formats with different cathode types such as LCO (LiCo02), NCA (LiNi0.8Co0.15Al0.05O2), LMO (LiMn204), NMC (LiNi0.33Mn0.33Co0.34O2) and LMO-NMC (LiNi0.2Mn0.54Co0.26O2), which can be recycled simultaneously to meet the demand of the electronic and automotive markets.

[0010] In addition, the present invention also aims to provide a lithium ion battery recycling method that employs the mechanical processing of the batteries without the need for any form of thermal treatment and without the use of a reducing agent during the leaching step.

[0011] ​​​​​​​Furthermore, the present application aims to provide a lithium-ion battery recycling method comprising a metal separation route by ozonation followed by electrodialysis, and a lithium-ion battery recycling method comprising a metal separation route by electrodialysis. SUMMARY

[0013] Aspects and advantages of the application will be set forth in part in the following description, can become apparent from the description, or can be learned by practice of the application.

[0014] In a first embodiment, the battery recycling method of the present application comprises the following steps:

[0015] - discharging the battery to be recycled;

[0016] - disassembling and separating the components of the battery, wherein the components are grouped into: electronic parts and protective casing, and battery cells;

[0017] - grinding the lithium-ion battery cells, wherein the grinding is performed in a cooling fluid;

[0018] - separating the plastic parts containing graphite and active material from the ground material obtained in the grinding step, wherein the plastic parts are washed and sieved to separate the plastic from the graphite and active material, the latter two being sent to leaching, the sieve used having a mesh size between 0.1 mm and 4 mm;

[0019] - precipitating the fluorides from the solution resulting from the separation step by adding or - removing the precipitated fluorides from the solution by filtering using a filter having a pore size in the range of 0.1 to 4 pm;

[0020] - precipitating the lithium from the solution resulting from the fluorides precipitation step by adding - removing the precipitated lithium from the solution by filtering using a filter having a pore size in the range of 0.1 to 4 pm;

[0021] - leaching the solids resulting from the grinding step and the physical separation step with an acid;

[0022] - filtering the leached solution using a filter having a pore size in the range of 0.1 to 4 pm to separate the leach liquor from the solid material;

[0023] - separating the solid material filtered in the previous step;

[0024] - Manganese is separated by ozonation of the leachate from the previous step, and then separated as manganese oxide by filtration using a filter with a pore size in the range of 0.1 to 4 µm.

[0025] - By joining or Aluminum is precipitated from the solution obtained by the ozonation step, wherein aluminum is precipitated in the form of aluminum oxide, aluminum hydroxide or aluminum carbonate, and aluminum is removed from the solution by filtration using a filter with a pore size in the range of 0.1 to 4 µm.

[0026] - Cobalt is extracted from the solution obtained from the aluminum precipitation step by solvent extraction in three sub-steps:

[0027] ○ Use phosphonates such as bis(2,4,4-trimethylpentyl)phosphonic acid, di-(2-ethylhexyl)phosphoric acid, trialkylphosphine, phosphonic acid, or phosphonic acid as extractants to form two phases, an aqueous phase and an organic phase.

[0028] ○ Discharge of aqueous phase, and

[0029] ○ The organic phase is fed into a container containing In the re-extraction solution, cobalt is extracted in the form of cobalt sulfate and removed from the solution by filtration using a filter with a pore size in the range of 0.1 to 4 µm;

[0030] - By joining or Nickel is precipitated from the solution obtained by the cobalt solvent extraction step, wherein the nickel is precipitated as nickel oxide, nickel hydroxide, or nickel carbonate, and the nickel is removed from the solution by filtration using a filter with a pore size in the range of 0.1 to 4 µm; and

[0031] - Precipitate the remaining lithium from the solution obtained from the nickel precipitation step, wherein the remaining lithium is... , , or The lithium is precipitated in the form of a precipitate and the remaining lithium is removed from the solution by filtration using a filter with a pore size in the range of 0.1 to 4 µm.

[0032] In additional or alternative embodiments of the lithium-ion battery recycling method according to the present invention, the following features and their possible variations may also exist individually or in combination:

[0033] - This method is applicable to LCO, NCA, NMC (111, 622, 532, 631, 811), LMO and LMO-NMC batteries in square, cylindrical and pouch forms;

[0034] - the discharging step is carried out in two sub-steps, wherein the electrical energy discharged from the battery can be recovered;

[0035] - the discharging step is carried out through a resistance;

[0036] - the grinding step is carried out using a shredder-type mill or a knife-type mill;

[0037] - the grinding step comprises a continuous addition of a cooling fluid, wherein the battery cells are inserted into the mill at intervals in the range of 1 to 20 seconds between individual pieces, and the ground material has a particle size of less than 50 mm;

[0038] - the cooling fluid used in the grinding step is preferably water;

[0039] - the separation step is carried out by at least one of decanting, centrifuging or a vibrating table;

[0040] - the sieve used has a mesh size of between 1 mm and 2 mm;

[0041] - in the fluorine precipitation step, with a reaction time of at most 2 hours and a temperature of between 25°C and 90°C, is added in an amount of between stoichiometric amount and 20% excess or ;

[0042] - in the lithium precipitation step, with a reaction time of at most 2 hours, a temperature of between 20°C and 80°C and a lithium precipitation yield of 10%, is added in an amount of between stoichiometric amount and 20% excess ;

[0043] - the acid used in the leaching step is selected from sulfuric acid, phosphoric acid or citric acid;

[0044] - the leaching step is carried out without a reducing agent;

[0045] - the leaching step is carried out with an acid concentration that can be in the range of 0.5 mol / L to 4.0 mol / L, preferably in the range of 0.7 mol / L to 2 mol / L, at a temperature of between 25°C and 90°C, preferably between 60°C and 90°C, and a reaction time in the range of 0.5 to 5 hours, preferably in the range of 1 to 3 hours;

[0046] - the solid material filtered in the filtration step of the leaching solution comprises graphite, remnants of the battery outer structure, metallic copper pieces and metallic aluminum pieces;

[0047] - the separation step is carried out by at least one of decanting, centrifuging, a vibrating table, sieving and elutriation;

[0048] - the sieve used in the previous separation step has a mesh size comprised between 0.03 mm and 4.0 mm;

[0049] - the sieve used in the previous separation step has a mesh size comprised between 1.5 mm and 3.0 mm;

[0050] - the elutriation in the separation step is carried out using a conventional elutriator;

[0051] - the ozonation step consists of the direct injection of ozone into the leachate leaving the leaching step to react with manganese ions, wherein ozone is generated from a generator and oxygen, and the step is carried out in a batch reactor or in a column in a continuous system, at a temperature between 10°C and 60°C, preferably between 15°C and 35°C, with an ozone gas flow rate between 0.2 L / min and 3.0 L / min, preferably between 0.6 L / min and 2.0 L / min;

[0052] - the aluminum precipitation step is carried out at a pH range between 3.0 and 5.0, at a temperature between 25°C and 80°C and for a reaction time between 0.5 and 3.0 hours;

[0053] - the cobalt solvent extraction step uses phosphinic acid, with a ratio between aqueous phase and organic phase between 1:5 and 5:1, a phosphinic acid concentration between 5% and 25% v / v and a temperature between 25°C and 60°C, carried out in countercurrent, to obtain a cobalt sulfate solution;

[0054] - the nickel precipitation step is carried out at a pH range between 5.0 and 9.0, at a temperature between 25°C and 80°C and for a reaction time between 0.5 and 3.0 hours;

[0055] - the residual lithium precipitation step is carried out by one of the following methods:

[0056] i) crystallization of the solution obtained from the nickel precipitation step, with a reaction time between 1.0 and 5.0 hours, at a temperature between 80°C and 110°C, to obtain lithium sulfate (Li2S04), ,

[0057] ii) addition of sodium phosphate (solid or in solution) to the solution, with a reaction time between 1.0 and 5.0 hours, at a temperature between 25°C and 90°C, under stirring, to obtain lithium phosphate (Li3P04), ,

[0058] o iii) adding sodium carbonate (solid or in solution) to the solution with a concentration between 50 g / L and 200 g / L at a temperature between 25°C and 90°C and a reaction time between 1.0 and 5.0 hours under stirring to obtain lithium carbonate ( ); or

[0059] o iv) adding calcium hydroxide to the lithium carbonate obtained in step iii) with a concentration between 0.2 g / L and 1.0 g / L at a temperature between 25°C and 90°C and a reaction time between 1.0 and 5.0 hours to obtain lithium hydroxide ( ).

[0060] - a step of separating aluminium from the solution by electrodialysis using cationic membranes, wherein the electrodialysis is carried out at a current in the range of 200 mA to 400 mA, with a current density in the range of 1.0 mA / cm² to 31.25 mA / cm² and a reaction time of up to 30 hours, and wherein the aluminium concentrated solution is subjected to an aluminium precipitation step and the remaining solution is subjected to a cobalt solvent extraction step;

[0061] - adding sodium oxalate ( ) or oxalic acid ( ) in an amount in the range of stoichiometric amount to 20% excess to the cobalt sulphate solution obtained from the cobalt solvent extraction step to obtain a precipitated cobalt oxalate in a 1:1 molar ratio, and subsequently:

[0062] o subjecting the solution containing cobalt oxalate to a calcination step at between 400°C and 800°C to obtain cobalt oxide, and optionally, adding (either in stoichiometric amount or up to 20% excess) at a temperature between 25°C and 80°C with a reaction time between 0.5 and 3.0 hours in the pH range of 6.0 to 10.0 to obtain cobalt carbonate; or

[0063] o subjecting the solution to electrolysis to obtain cobalt in metallic form,

[0064] o wherein the cobalt oxide, cobalt carbonate and metallic cobalt are removed from the solution by filtration using filters with a pore size in the range of 0.1 to 4 μm;

[0065] - using filters with a pore size of 1 to 2 μm in the filtration to remove cobalt oxide, cobalt carbonate and metallic cobalt from the solution;

[0066] - after the remaining lithium precipitation step, the solution is subjected to a crystallization step to obtain sodium sulphate crystals, and the acid used in the leaching step is recovered and returned to the leaching step;

[0067] - the filters used have a pore size between 1 and 2 pm in the fluorine precipitation step, lithium precipitation step, leaching step, filtration step of the leaching solution, ozonation step, aluminium precipitation step, cobalt solvent extraction step, nickel precipitation step and residual lithium precipitation step;

[0068] - the filters used are of paper or membrane type.

[0069] In an alternative embodiment, the battery recycling method of the present application does not comprise an ozonation step for the separation of manganese, wherein manganese is separated together with cobalt in the solvent extraction step. This alternative embodiment of the present application comprises the following steps:

[0070] - discharging the battery to be recycled;

[0071] - disassembling and separating the components of the battery, wherein the components are grouped into: electronic parts and protective casing, and battery cells;

[0072] - grinding the battery cells, wherein the grinding is carried out in a cooling fluid;

[0073] - separating the plastic parts with graphite and active material from the ground material obtained in the grinding step, wherein the plastic parts with graphite and active material are washed and sieved to separate graphite and active material, the graphite and active material are leached and the sieve used has a mesh size between 0.1 mm and 4 mm;

[0074] - precipitating fluorine from the solution obtained in the separation step by adding or wherein the precipitated fluorine is removed from the solution by filtering using filters having a pore size between 0.1 pm and 4 pm;

[0075] - precipitating lithium from the solution obtained in the fluorine precipitation step by adding wherein the precipitated lithium is removed from the solution by filtering using filters having a pore size between 0.1 pm and 4 pm;

[0076] - leaching the solid material obtained from the grinding step and physical separation step with an acid;

[0077] - filtering the leaching solution using filters having a pore size between 0.1 pm and 4 pm to separate the leachate and the solid material;

[0078] - separating the solid material filtered in the leaching step;

[0079] - precipitating fluorine from the solution obtained in the leaching step by adding or precipitating the aluminium from the solution obtained in the leaching step, wherein the aluminium is precipitated in the form of aluminium oxide, aluminium hydroxide or aluminium carbonate and is removed from the solution by filtration using a filter having a pore size between 0.1 pm and 4 pm;

[0080] - extracting cobalt and manganese from the solution obtained in the aluminium precipitation step by solvent extraction in six sub-steps:

[0081] o extracting cobalt and manganese from the solution using a phosphine oxide such as bis(2,4,4-trimethylpentyl) phosphinic acid, di-(2-ethylhexyl) phosphonic acid, trialkyl phosphine, phosphonic acid or phosphinic acid, resulting in two phases, one aqueous phase and one organic phase, the aqueous phase being discharged,

[0082] o extracting cobalt and manganese from the solution using a phosphine oxide such as bis(2,4,4-trimethylpentyl) phosphinic acid, di-(2-ethylhexyl) phosphonic acid, trialkyl phosphine, phosphonic acid or phosphinic acid, resulting in two phases, one aqueous phase and one organic phase, the aqueous phase being discharged, o stripping cobalt and manganese from the organic phase of the previous sub-step, wherein the cobalt is recovered in the form of cobalt sulphate in an aqueous phase and the manganese is recovered in the form of manganese sulphate in an aqueous phase,

[0083] o extracting manganese from the solution obtained in the previous sub-step using a phosphine oxide such as bis(2,4,4-trimethylpentyl) phosphinic acid, di-(2-ethylhexyl) phosphonic acid, trialkyl phosphine, phosphonic acid or phosphinic acid, resulting in two phases, one phase containing cobalt and one phase containing manganese, the aqueous phase containing cobalt being directed to cobalt precipitation,

[0084] o extracting manganese from the solution obtained in the previous sub-step using a phosphine oxide such as bis(2,4,4-trimethylpentyl) phosphinic acid, di-(2-ethylhexyl) phosphonic acid, trialkyl phosphine, phosphonic acid or phosphinic acid, resulting in two phases, one phase containing cobalt and one phase containing manganese, the aqueous phase containing cobalt being directed to cobalt precipitation, o stripping manganese from the organic phase of the solution of the previous sub-step, wherein the manganese is recovered in the form of manganese sulphate in an aqueous phase, and

[0085] o precipitating manganese from the aqueous phase of the previous sub-step using a reagent , , or , wherein the manganese is precipitated in the form of manganese hydroxide, manganese oxalate or manganese carbonate and is removed from the solution by filtration using a filter having a pore size between 0.1 pm and 4 pm,

[0086] o precipitating cobalt from the aqueous phase of the solution of the manganese solvent extraction sub-step using a reagent , oxalic acid, sodium oxalate or , wherein the cobalt is precipitated in the form of cobalt hydroxide, cobalt oxalate or cobalt carbonate and is removed from the solution by filtration using a filter having a pore size between 0.1 pm and 4 pm;

[0087] - by adding or precipitating nickel from the solution obtained in the cobalt and manganese solvent extraction step, wherein the nickel is precipitated in the form of nickel oxide, nickel hydroxide or nickel carbonate and is removed from the solution by filtration using a filter with a pore size between 0.1 pm and 4 pm; and

[0088] - precipitating the remaining lithium from the solution obtained in the nickel precipitation step, wherein the remaining lithium is precipitated in the form of lithium carbonate, lithium hydroxide or lithium oxide and is removed from the solution by filtration using a filter with a pore size between 0.1 pm and 4 pm. 、 、 or .

[0089] According to additional or alternative embodiments of the alternative embodiments of the battery recycling method according to the present application, the following features and possible variants thereof can also be present, either individually or in combination:

[0090] - the step of separating aluminium from the solution by electrodialysis with cationic membranes, wherein the electrodialysis is carried out with a current in the range of 200 mA to 400 mA, a current density of 1.0 mA / cm2to 31.25 mA / cm2and a reaction time of up to 30 hours, and wherein the aluminium concentrated solution is subjected to the aluminium precipitation step and the remaining solution is subjected to the step of extracting cobalt and manganese by solvent extraction;

[0091] - the solvent extraction sub-step is carried out in a countercurrent manner at a temperature range between 25°C and 60°C, with a ratio between the aqueous phase and the organic phase between 1 :5 and 5:1 and a phosphinic acid concentration between 5% and 25% v / v;

[0092] - the stripping sub-step is carried out in a countercurrent manner at a temperature range between 25°C and 60°C, with a ratio between the aqueous phase and the organic phase between 1 :5 and 5:1 and a sulphuric acid concentration between 0.1 mol / L and 5.0 mol / L;

[0093] - the manganese and cobalt precipitation sub-step is carried out at a pH range between 6.0 and 10.0, a reaction time between 0.5 and 3.0 hours and a temperature between 25°C and 80°C, with the addition of a reagent in an amount ranging from the stoichiometric amount to an excess of 20%;

[0094] - the manganese oxalate and the cobalt oxalate are subjected to a calcination step at a temperature between 400°C and 800°C to obtain cobalt oxide and manganese oxide.

[0095] The method for resynthesizing cathode active materials for batteries can be performed from the material after separation or directly from the leach obtained in the leaching step. Cathode materials that can be synthesized directly from the leach include NCA, LMO, LCO, NMC and LMO-NMC.

[0096] The method for direct resynthesis from the leach can be performed by utilizing and co-precipitation at a temperature ranging from 25°C to 90°C for 0.5 to 12 hours. Then, the resulting solid is subjected to a heat treatment in air or inert atmosphere at 200°C to 500°C for 0.5 to 12 hours followed by a calcination step in inert atmosphere, air or oxygen atmosphere at 600°C to 800°C for 0.5 to 12 hours.

[0097] In an alternative embodiment, after the acid leaching and filtration steps of the previous embodiment, the battery recycling method of the invention separates the metals by ozonation followed by electrodialysis. This alternative embodiment of the invention comprises the following steps:

[0098] - discharging the battery to be recycled;

[0099] - disassembling and separating the components of the battery, wherein the components are grouped into: electronic parts and protective structure, and battery cells;

[0100] - grinding the lithium-ion battery cells, wherein said grinding is performed in a cooling fluid;

[0101] - separating the plastic parts containing graphite and active material from the ground material resulting from the grinding step, wherein said plastic parts containing graphite and active material are subjected to washing and sieving to separate graphite and active material, the graphite and active material being directed to the leaching step, the sieves used having a mesh size between 0.1 mm and 4 mm;

[0102] - precipitating fluorine from the solution resulting from the separation step by adding or removing the precipitated fluorine from the solution by filtering (116) using a filter having a pore size of 0.1 pm to 4 pm;

[0103] - precipitating lithium from the solution resulting from the fluorine precipitation step by adding removing the precipitated lithium by filtering using a filter having a pore size of 0.1 pm to 4 pm;

[0104] - leaching the solid obtained from the grinding step and the physical separation step with an acid;

[0105] - filtering the leaching solution using a filter having a pore size of 0.1 pm to 4 pm to separate the leachate and the solid material;

[0106] - isolating the solid material filtered in the previous step;

[0107] - treating the leach liquor from the previous step by ozonation to isolate manganese, wherein the manganese is isolated in the form of manganese oxide by filtration using a filter with a pore size of 0.1 pm to 4 pm, or isolated by precipitation using a precipitating agent such as sodium hypochlorite, or isolated by electrodeposition (in the form of an oxide);

[0108] - subjecting the solution resulting from the ozonation step to lithium isolation by electrodialysis using a monovalent membrane, wherein the electrodialysis is performed at a current of between 10 mA and 400 mA, preferably between 10 mA and 70 mA, with a current density of 0.1 mA / cm2to 25 mA / cm2, preferably 12.5 mA / cm2to 25 mA / cm2, and a reaction time of 20 hours to 160 hours, preferably up to 30 hours, wherein the lithium concentrated solution is subjected to a lithium recovery step by precipitation, and the remaining solution is subjected to a subsequent electrodialysis step;

[0109] - subjecting the solution obtained from the lithium isolation step to a nickel isolation step by complexation with ethylenediaminetetraacetic acid (EDTA), followed by electrodialysis using a cationic membrane in a system comprising a cationic membrane and an anionic membrane (an anion exchange membrane), wherein the electrodialysis is performed at a current of 100 mA to 500 mA, preferably 200 mA to 400 mA, with a current density of 1.0 mA / cm2to 31.25 mA / cm2, preferably 12.5 mA / cm2to 25 mA / cm2, and a reaction time of 20 hours to 160 hours, preferably up to 30 hours, and wherein the nickel concentrated solution is subjected to a nickel recovery step by precipitation or electrodeposition (in the form of a metal), and the remaining solution is subjected to a new electrodialysis step; and

[0110] - subjecting the solution from the nickel isolation step to a cobalt and aluminium isolation step by complexation with 1-hydroxyethane-1,1-diphosphonic acid (HEDP), followed by electrodialysis using a cationic membrane in a system comprising a cationic membrane and an anionic membrane, wherein the electrodialysis is performed at a current of 100 mA to 500 mA, preferably 200 mA to 400 mA, with a current density of 1.0 mA / cm2to 31.25 mA / cm2, preferably 12.5 mA / cm2to 25 mA / cm2, and a reaction time of 20 hours to 160 hours, preferably up to 30 hours, thereby producing two different solutions, which are subjected to respective recovery steps by precipitation or electrodeposition of cobalt (in the form of a metal) and aluminium (in the form of a metal).

[0111] According to additional or alternative embodiments of the battery recycling method of the present application, the following features and possible variants thereof can also be present, alone or in combination:

[0112] - the method is suitable for batteries containing manganese, or in the absence of manganese, the method can be carried out without ozonation. Example batteries include those selected from the group consisting of NMC (1 1 1, 622, 532, 631, 81 1 ), LMO, LMO-NMC and NCA of square, cylindrical and / or prismatic type, or pouch type;

[0113] - the discharging step can be carried out in two sub-steps, allowing the recovery of the electrical energy discharged from the battery;

[0114] - the discharging step can be carried out using an electrical resistance;

[0115] - the grinding step can be carried out using a shredder-type grinder or a blade-type grinder;

[0116] - the grinding step comprises the continuous addition of a cooling fluid, wherein the battery cells are inserted into the grinder at intervals of between 1 and 20 seconds between individual parts, and the ground material has a particle size of less than 50 mm;

[0117] - the cooling fluid used in the grinding step is preferably water;

[0118] - the separation step is carried out using at least one of decanting, centrifugation or a vibrating table;

[0119] - the sieve used has a mesh size of between 1 and 2 mm;

[0120] - in the fluorine precipitation step, with a reaction time of up to 2 hours and a temperature of between 25 and 90°C, the amount of or added is in the range of stoichiometric amount to 20% excess;

[0121] - in the lithium precipitation step, with a reaction time of up to 2 hours, a temperature of between 20 and 80°C and a lithium precipitation yield of 10%, the amount of is added in the range of stoichiometric amount to 20% excess;

[0122] - the acid used in the leaching step is selected from sulfuric acid, phosphoric acid or citric acid;

[0123] - the leaching step is carried out without a reducing agent;

[0124] - the leaching step is carried out with an acid concentration ranging from 0.5 mol / L to 4.0 mol / L, preferably ranging from 0.7 mol / L to 2 mol / L, at a temperature between 25°C and 90°C, preferably between 60°C and 90°C, with a reaction time of 0.5 to 5 hours, preferably 1 to 3 hours;

[0125] - the solid material filtered from the leaching solution comprises graphite, residues of the outer cell structure, metallic copper pieces and metallic aluminum pieces;

[0126] - the separation step is carried out using at least one of decantation, centrifugation, shaking table, sieving and elutriation;

[0127] - the sieve used in the previous separation step has a mesh size between 0.03 mm and 4.0 mm;

[0128] - preferably, the sieve has a mesh size between 1.5 mm and 3.0 mm;

[0129] - the elutriation is carried out in a conventional elutriator;

[0130] - the ozonation step consists of injecting ozone directly into the leaching solution to react with the manganese ions, wherein the ozone is generated from a generator and oxygen, and the step is carried out in a batch reactor or in a column in a continuous system, with a gas flow rate of 0.2 L / min to 3.0 L / min, preferably 0.6 L / min to 2.0 L / min, and at a temperature between 10°C and 60°C, preferably between 15°C and 35°C;

[0131] - lithium is precipitated in the form of , , or and is removed by filtration using a filter with a pore size of 0.1 pm to 4 pm;

[0132] - the lithium precipitation is carried out by one of the following methods:

[0133] o i) crystallization at 80°C to 110°C for 1.0 to 5.0 hours to obtain lithium sulfate (Li2SO4) ; );

[0134] o ii) addition of sodium phosphate (solid or solution) under stirring at 25°C to 90°C for 1.0 to 5.0 hours to obtain lithium phosphate (Li3PO4) ;

[0135] ​o iii) adding sodium carbonate (solid or solution) at a concentration of 50 g / L to 200 g / L at a temperature of 25 °C to 90 °C for 1.0 to 5.0 hours to obtain lithium carbonate ( );

[0136] o iv) converting lithium carbonate from process iii) to lithium hydroxide ( );

[0137] - precipitating nickel by adding or nickel oxide, nickel hydroxide or nickel carbonate and removing nickel by filtration using a filter with a pore size of 0.1 pm to 4 pm;

[0138] - nickel precipitation is carried out at a pH of 5.0 to 9.0, at a temperature of 25 °C to 80 °C for 0.5 to 3.0 hours;

[0139] - precipitating aluminum by adding or aluminum oxide, aluminum hydroxide or aluminum carbonate and removing aluminum by filtration using a filter with a pore size of 0.1 pm to 4 pm;

[0140] - aluminum precipitation is carried out at a pH of 3.0 to 5.0, at a temperature of 25 °C to 80 °C for 0.5 to 3.0 hours;

[0141] - precipitating cobalt by adding at a pH of 6 to 10, in a reaction time of 30 minutes to 3 hours and at 25 °C. Filtration is carried out using a 2 pm filter;

[0142] - electrodeposition of nickel (in metallic form) is carried out using methods known to the person skilled in the art;

[0143] - electrodeposition of manganese (in oxide form) is carried out using known techniques;

[0144] - electrodeposition of cobalt (in metallic form) is carried out in an electrolysis cell at a potential difference between cathode and anode of 2 to 4 V, a current density of 60 to 400 A / m2, a temperature of 40 °C to 70 °C, a liquid with a pH value of from 2 to 5, an initial cobalt concentration of more than 9 g / L, a final cobalt concentration of between 4 and 6 g / L;

[0145] - electrodeposition of aluminum (in metallic form) is carried out using known procedures;

[0146] - after the lithium precipitation, the solution can be crystallized to obtain sodium sulfate crystals, recovering the acid used in the leaching for reuse;

[0147] - in the fluorine precipitation step, the lithium precipitation step, the leaching step, the filtration step of the leaching solution, the ozonation step, the aluminum precipitation step, the cobalt precipitation step, the nickel precipitation step and the lithium precipitation step, filters with a pore size between 1 and 2 pm are used;

[0148] - the filters used are of paper or membrane type.

[0149] In another alternative embodiment, after the acid leaching and filtration steps of the first and second embodiments, the battery recycling method of the present application does not comprise the ozonation step and all the metals are separated by electrodialysis. This alternative embodiment of the present application comprises the following steps:

[0150] - discharging the batteries to be recycled;

[0151] - disassembling and separating the components of the batteries, grouping the components into: electronic parts and protective structure, and battery cells;

[0152] - grinding the lithium-ion battery cells, wherein the grinding is carried out in a cooling fluid;

[0153] - separating the plastic parts with graphite and active material from the ground material obtained from the grinding step, wherein the plastic parts with graphite and active material are washed and sieved to separate the graphite and active material, the graphite and active material are leached, and the sieve used has a mesh between 0.1 and 4 mm;

[0154] - precipitating the fluorine from the solution obtained in the separation step by adding or removing the precipitated fluorine from the solution by filtering (116) using a filter with a pore size in the range of 0.1 to 4 pm;

[0155] - precipitating the lithium from the solution obtained in the fluorine precipitation step by adding removing the precipitated lithium from the solution by filtering using a filter with a pore size of 0.1 to 4 pm;

[0156] - leaching the solids obtained from the grinding step and the physical separation step with an acid;

[0157] - filtering the leaching solution using a filter with a pore size of 0.1 to 4 pm to separate the leachate and the solid material;

[0158] - separating the solid material filtered in the previous step;

[0159] - performing a lithium separation step on the leach solution from the previous step by using monovalent membrane electrodialysis, wherein the electrodialysis is performed at a current range of 10 mA to 400 mA, preferably 10 mA to 70 mA, with a current density of 0.1 mA / cm2to 25 mA / cm2, preferably 12.5 mA / cm2to 25 mA / cm2, and a reaction time of 20 hours to 160 hours, preferably up to 30 hours, wherein the lithium concentrated solution is subjected to a lithium recovery step by precipitation and the remaining solution is subjected to a new electrodialysis step;

[0160] - complexing the solution from the lithium separation step with ethylenediaminetetraacetic acid (EDTA) followed by a nickel separation step by using cationic membrane electrodialysis in a system comprising cationic and anionic membranes, wherein the electrodialysis is performed at a current range of 100 mA to 500 mA, preferably 200 mA to 400 mA, with a current density of 1.0 mA / cm2to 31.25 mA / cm2, preferably 12.5 mA / cm2to 25 mA / cm2, and a reaction time of 20 hours to 160 hours, preferably up to 30 hours, wherein the nickel concentrated solution is subjected to a nickel recovery step by precipitation or electrodeposition (as metal) and the remaining solution is subjected to a new electrodialysis step;

[0161] - complexing the solution from the nickel separation step with ethylenediaminetetraacetic acid (EDTA) followed by a manganese separation step by using cationic membrane electrodialysis in a system comprising cationic and anionic membranes, wherein the electrodialysis is performed at a current range of 100 mA to 500 mA, preferably 200 mA to 400 mA, with a current density of 1.0 mA / cm2to 31.25 mA / cm2, preferably 12.5 mA / cm2to 25 mA / cm2, and a reaction time of 20 hours to 160 hours, preferably up to 30 hours, wherein the manganese concentrated solution is subjected to a manganese recovery step by precipitation or electrodeposition (as oxide) and the remaining solution is subjected to a new electrodialysis step; and

[0162] - the solution coming from the manganese separation step is complexed with 1-hydroxyethane-1,1-diphosphonic acid, followed by a cobalt and aluminium separation step by electrodialysis using the cationic membrane in a system comprising a cationic membrane and an anionic membrane, wherein the electrodialysis is carried out at a current ranging from 100 mA to 500 mA, preferably from 200 mA to 400 mA, with a current density ranging from 1.0 mA / cm2to 31.25 mA / cm2, preferably from 12.5 mA / cm2to 25 mA / cm2, and a reaction time ranging from 20 hours to 160 hours, preferably up to 30 hours, and two different solutions are obtained, which are subjected to a recovery step by precipitation or electrodeposition of cobalt (in metallic form) and precipitation or electrodeposition of aluminium (in metallic form).

[0163] According to further or alternative embodiments of the battery recycling method according to the present application, the following features and possible variants thereof can also be present, alone or in combination:

[0164] - the method is suitable for batteries containing manganese in their composition, or even without the need to carry out ozonation if manganese is not present. Examples include batteries selected from the group consisting of NMC (1 1 1, 622, 532, 631, 81 1 ), LMO, LMO-NMC and NCA, wherein the battery type is square, cylindrical and / or prismatic;

[0165] - the discharging step is carried out in two sub-steps, making it possible to recover the electrical energy discharged from the battery;

[0166] - the discharging step is carried out by means of a resistance;

[0167] - the grinding step is carried out in a shredder-type grinder or a blade-type grinder;

[0168] - the grinding step comprises the continuous addition of a cooling fluid, wherein the battery cells are inserted into the grinder at intervals of between 1 and 20 seconds between each part, and the ground material has a particle size of less than 50 mm;

[0169] - the cooling fluid in the grinding step is preferably water;

[0170] - the separation step is carried out by at least one of decanting, centrifuging or a vibrating table;

[0171] - the sieve used has a mesh size of between 1 and 2 mm;

[0172] - in the fluorine precipitation step, the addition of or is carried out in an amount of between stoichiometric amount and 20% excess, with a reaction time of up to 2 hours and a temperature of between 25°C and 90°C;

[0173] - in the lithium precipitation step, the quantity of lithium precipitated is between the stoichiometric quantity and 20% excess; - the quantity of lithium added is between the stoichiometric quantity and 20% excess;

[0174] - the acid used in the leaching step is selected from one of sulfuric acid, phosphoric acid or citric acid;

[0175] - the leaching step is carried out without a reducing agent;

[0176] - the leaching step is carried out with an acid concentration that can range from 0.5 mol / L to 4.0 mol / L, preferably from 0.7 mol / L to 2 mol / L, using a temperature between 25°C and 90°C, preferably between 60°C and 90°C, and a reaction time of 0.5 to 5 hours, preferably 1 to 3 hours;

[0177] - the solid material filtered in the filtration step of the leaching solution comprises graphite, residues of the external structure of the battery, metallic copper pieces and metallic aluminum pieces;

[0178] - the separation step is carried out by at least one of decantation, centrifugation, shaking table, sieving and elutriation;

[0179] - the sieve used in the separation step described above has a mesh size between 0.03 and 4.0 mm;

[0180] - the sieve used in the separation step described above has a mesh size between 1.5 and 3.0 mm;

[0181] - the elutriation in the separation step is carried out in a conventional elutriator;

[0182] - the lithium is precipitated in the form of , , or and is removed from the solution by filtration using a filter with a pore size of 0.1 to 4 pm;

[0183] - the lithium precipitation step is carried out by one of the following methods:

[0184] o i) the solution is crystallized at a temperature of 80°C to 110°C for 1.0 to 5.0 hours to obtain lithium sulfate (Li2S04); o ii) sodium phosphate (solid or in solution) is added to the solution under stirring at a temperature of 25°C to 90°C for 1.0 to 5.0 hours to obtain lithium phosphate (Li3P04);

[0185] o ii) sodium phosphate (solid or in solution) is added to the solution under stirring at a temperature of 25°C to 90°C for 1.0 to 5.0 hours to obtain lithium phosphate (Li3P04);

[0186] ​○ iii) Sodium carbonate (solid or in solution) is added to the solution at a concentration of 50 g / L to 200 g / L at a temperature of 25°C to 90°C for 1.0 to 5.0 hours with stirring to obtain lithium carbonate ( );or

[0187] ○ iv) At a temperature of 25°C to 90°C, calcium hydroxide is added to the lithium carbonate obtained in section iii) at a concentration of 0.2 g / L to 1.0 g / L for 1.0 to 5.0 hours to obtain lithium hydroxide ( );

[0188] - By joining or Nickel is precipitated from the solution in the form of nickel oxide, nickel hydroxide, or nickel carbonate, and removed from the solution by filtration using a filter with a pore size of 0.1 to 4 µm.

[0189] - The nickel precipitation step was carried out in a pH range of 5.0 to 9.0, a temperature of 25°C to 80°C, and a reaction time of 0.5 to 3.0 hours;

[0190] - The manganese precipitation step using ozone, which can occur in a batch reactor or in a column in a continuous system, with a gas flow rate of 0.2 L / min to 4.0 L / min, preferably 0.6 L / min to 2.0 L / min, at a temperature range of 10°C to 60°C, preferably 15°C to 35°C, results in precipitation;

[0191] - By joining or Precipitated aluminum, wherein aluminum is precipitated in the form of aluminum oxide, aluminum hydroxide or aluminum carbonate, and aluminum is removed from the solution by filtration using a filter with a pore size of 0.1 to 4 µm;

[0192] - The aluminum precipitation step was carried out in a pH range of 3.0 to 5.0, a temperature of 25°C to 80°C, and a reaction time of 0.5 to 3.0 hours;

[0193] - The cobalt precipitation step involves adding [cobalt] at a pH of 6 to 10 and a temperature of 25°C. Perform the test for 30 minutes to 3 hours. Filter using a 2 µm filter to retain the solid phase (cobalt salt / product).

[0194] - The nickel electrodeposition step (in metallic form) is performed using procedures known to those skilled in the art;

[0195] - The manganese electrodeposition step (in oxide form) is performed using procedures known to those skilled in the art;

[0196] - the cobalt electrodeposition step (in metallic form) is operated in an electrodeposition cell, with a potential difference between cathode and anode of 2 to 4 V, a current density of 60 to 400 A / m2, a temperature of 40°C to 70°C, a liquid with a pH value adjusted from 2 to 5, an initial cobalt concentration higher than 9 g / L and a final concentration between 4 and 6 g / L;

[0197] - the aluminum electrodeposition step (in metallic form) is carried out by procedures known to the person skilled in the art;

[0198] - after the lithium precipitation step, the solution undergoes a crystallization step to obtain sodium sulfate crystals, and the acid used in the leaching is recovered for reuse in the leaching step;

[0199] - in the fluorine precipitation step, lithium precipitation step, leaching step, filtration step of the leaching solution, aluminum precipitation step, cobalt precipitation step, nickel precipitation step, manganese precipitation step and remaining lithium precipitation step, the filters used have a pore size between 1 and 2 pm;

[0200] - the filters used are of paper or membrane type.

[0201] The method for resynthesizing the active cathode material of the battery can be carried out from the material after separation or directly from the leachate. The cathodes that can be synthesized directly from the leachate include NCA, LMO, LCO, NMC and LMO-NMC.

[0202] The method for direct resynthesis from the leachate can be carried out by using and at a temperature between 25°C and 90°C for 0.5 to 12 hours. Then, the resulting solid is subjected to a heat treatment in air or inert atmosphere at 200°C to 500°C for 0.5 to 12 hours, followed by a calcination step in inert atmosphere, air or oxygen atmosphere at 600°C to 800°C for 0.5 to 12 hours. BRIEF DESCRIPTION OF DRAWINGS

[0203] There is a complete and enabling disclosure of the application, including the best mode thereof, to one of ordinary skill in the art, in the specific embodiment with reference to the drawings, wherein:

[0204] - Figure 1 a flowchart illustrating a first embodiment of the battery recycling method of the present application;

[0205] - Figure 2 a flowchart illustrating a second embodiment of the battery recycling method of the present application;

[0206] - Figure 3Figure 3 illustrates a flow chart of a third embodiment of the battery recycling method of the present application;

[0207] - Figure 4 Figure 4 illustrates a flow chart of a fourth embodiment of the battery recycling method of the present application;

[0208] - Figure 5 Figure 5 illustrates a flow chart of the cobalt and manganese solvent extraction step as shown in the flow charts of Figure 3 and Figure 4 Figure 6 illustrates a flow chart of the cobalt and manganese solvent extraction step as shown in the flow charts of

[0209] - Figure 6 Figure 7 illustrates a flow chart of the ozonation and electrodialysis steps for metal separation occurring after the acid leaching and filtration steps as shown in Figures 1 to 4 ; and

[0210] - Figure 7 Figure 8 illustrates a flow chart of the electrodialysis step for metal separation occurring after the acid leaching and filtration steps as shown in Figures 1 to 4 . DETAILED DESCRIPTION

[0211] Reference will now be made in detail to embodiments of the present application, one or more examples of which are illustrated in the drawings. Each example is provided by way of explanation of the present application, not limitation of the present application. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the present application without departing from the scope or spirit of the present application. For instance, the functions illustrated or described as part of some embodiments can be combined with functions of other embodiments to produce additional embodiments. Thus, it is intended that the present application cover such modifications and variations of this application provided they come within the scope of the appended claims and their equivalents.

[0212] Generally, as shown in Figure 1 , the battery recycling method 100 comprises the following steps: discharging 101 the batteries to be recycled, wherein the discharging can be performed, for example, by means of electrical resistance; disassembling and separating 102 the battery components, wherein the components are grouped into: electronic parts and protective casing, and battery cells; grinding 103 the battery cells, wherein the grinding is performed in a coolant fluid using a shredder-type grinder or a blade-type grinder, for example, to a particle size of 1 to 2 mm; separating 104 the ground material from the grinding step by means of at least one of decantation, centrifugation or a vibrating table, to separate the plastic parts with graphite and active material made of polypropylene and high-density polyethylene or low-density polyethylene, wherein the plastic parts with graphite and active material are washed under the condition of continuous addition of water and sieved 115 to separate the remaining graphite and active material. The sieve mesh is between 0.1 and 4 mm, preferably between 1 and 2 mm; by adding or Fluorine is precipitated from the solution obtained in step 104 105, wherein the precipitated fluorine is removed by filtration 116 using a filter with a pore size of 0.1 to 4 μm; by adding Lithium 106 is precipitated from the solution obtained in step 105, wherein the precipitated lithium is removed by filtration 117 using a filter with a pore size of 0.1 to 4 μm. As can be seen, the battery to be recycled is mechanically processed in a coolant fluid (e.g., water) without any heat treatment prior to leaching. Subsequently, the following steps are performed: the solids obtained from the grinding and physical separation steps are leached using an acid selected from sulfuric acid, phosphoric acid, or citric acid; the leachate is filtered 108 using a filter with a pore size of 0.1 to 4 µm to separate the leachate and solid materials, including graphite, residues from the external structure of the battery, copper flakes, and aluminum flakes; the solids 109 filtered from step 108 are separated, for example, using at least one of decantation, centrifugation, shaking table, sieving, and panning. Furthermore, step 109 uses a sieve with a mesh size between 0.03 and 4.0 mm, preferably between 1.5 and 3.0 mm; panning is performed using a conventional panning apparatus. The leachate is treated by ozonation 110 to separate manganese. The ozonation method consists of injecting ozone into the leachate output from step 108 to increase the redox potential of the solution and precipitate manganese. Ozone is generated by a generator and oxygen, and injected directly into the solution to react with manganese ions. After ozonation 110, manganese is separated as manganese oxide by filtration using a filter with a pore size of 0.1 to 4 μm; by adding... or Aluminum 111A is precipitated from the solution obtained in the ozonation step 110, wherein the aluminum is precipitated in the form of aluminum oxide, aluminum hydroxide, or aluminum carbonate, and the aluminum is removed from the solution by filtration using a filter with a pore size of 0.1 to 4 μm. Cobalt 112A is extracted from the solution obtained in the aluminum precipitation step 111A using a solvent in three sub-steps: a) using a phosphonic acid (e.g., bis(2,4,4-trimethylpentyl)phosphonic acid, bis(2-ethylhexyl)phosphonic acid, trialkylphosphine, phosphonic acid, or phosphonic acid) as an extractant to form two phases: an aqueous phase and an organic phase; b) discharging the aqueous phase; and c) transferring the organic phase to a container with… In the back-extraction solution, cobalt is extracted as cobalt sulfate and removed by filtration using a filter with a pore size of 0.1 to 4 μm. Next, by adding... or Nickel 113 is precipitated from the solution obtained in cobalt extraction step 112A, wherein the nickel is precipitated in the form of nickel oxide, nickel hydroxide, or nickel carbonate, and the nickel is removed by filtration using a filter with a pore size of 0.1 to 4 μm; residual lithium 114 is precipitated from the solution obtained after nickel precipitation step 113, wherein the residual lithium is precipitated in the form of nickel oxide, nickel hydroxide, or nickel carbonate. , , or precipitate in the form of and the remaining lithium is removed by filtration using a filter with a pore size of 0.1 to 4 pm. In all the steps described above - fluorine precipitation step 105, lithium precipitation step 106, leaching step 107, filtration step 108 of the leaching solution, ozonation step 110, aluminum precipitation step 111A, cobalt solvent extraction step 112A, nickel precipitation step 113 and remaining lithium precipitation step 114 - the filter used preferably has a pore size of 1 to 2 pm and can be of paper or membrane type.

[0213] The method 100 of the present application is applicable to LCO, NCA and NMC batteries of square, cylindrical and pouch type (types 111, 622, 532, 631, 811) and also LMO and LMO-NMC batteries. The method can also recycle simultaneously different types of these batteries. Regarding the type of batteries, this method has proven the feasibility of recycling batteries of different cathode materials (active materials) and configurations (pouch, cylindrical or square) in a single process. In addition, this method does not employ thermal treatments during the mechanical processing of the batteries, which is innovative in the recycling field. Furthermore, it has been shown that electrical energy can be recovered by the discharging step implemented in the present application, since it does not use a brine solution as in the prior art, which causes corrosion and thus loss of material.

[0214] The discharging step 101 is carried out in two sub-steps, both of which can be performed using resistors to eliminate residual electrical energy or to recover electrical energy. Illustratively, the discharging step 101 can be performed using Ni-Cr and metallic Cu resistors connected in series or in parallel to the terminals of the batteries for a period of 12 to 24 hours. The grinding step 102 includes the continuous addition of a cooling fluid, preferably water (wet grinding, which avoids the risk of explosions, unlike the prior methods). The battery cells are inserted into the grinder at intervals of 1 to 20 seconds between the various parts, and the ground material has a particle size of less than 50 mm. In the fluorine precipitation step 105, the amount of or between the stoichiometric amount and a 20% excess, with a reaction time of 2.0 hours, reaching a fluorine precipitation efficiency of up to 99%. In the lithium precipitation step 106, at 80°C, the amount of between the stoichiometric amount and a 20% excess, with a reaction time of 2.0 hours and a lithium precipitation efficiency of at least approximately 10%. The remaining lithium still present in the solution can be removed at the end of the process in a specific step 114 for the precipitation of the remaining lithium.

[0215] In the present invention, the outer structure of the battery cell, aluminum, graphite, active material, aluminum foil and copper foil and cathode (from all types of batteries) are directed to an acid leaching step 107 using an acid concentration in the range of 0.5 mol / L to 4.0 mol / L, preferably in the range of 0.7 mol / L to 2 mol / L, at a temperature between 25°C to 90°C, preferably between 60°C to 90°C and a reaction time between 0.5 to 5.0 hours, preferably between 1 to 3 hours. Regarding the leaching step 107, the key distinguishing feature of the present invention is the absence of a reducing agent. Due to the presence of the metallic aluminum foil from the battery cell, the leaching efficiency of the present invention can reach up to 99% of the metals present in the active material even in the absence of a reducing agent. The efficiency of the present invention is shown in Table 1 which provides a comparison between the results obtained with the claimed method and the results of the state of the art methods using a reducing agent or different types of acids than those employed in the method of the present invention.

[0216] Table 1

[0217]

[0218] Table 1 reference: （a） : 99% of aluminum leached from the active material and 70% of aluminum leached considering both the active material and the current collector foil; （b） : Iron contamination during the leaching step; （c） : The authors evaluated fruit juices (orange, pear, lemon, apple and banana) as leaching agents; （d） : https: / / linkinghub.elsevier.com / retrieve / pii / S0304386X21001547. Direct leaching of the active material, which is not a battery processing.

[0219] The liquid obtained in the leaching step 107 contains the metals manganese, aluminum, cobalt, nickel and lithium (85% of the elements present in the battery and remaining after step 106). After the leaching step 107, a filtration 108 is carried out to separate the leachate from the solid material. The solid material filtered in step 108 includes graphite, residues of the outer structure of the battery, metallic copper sheets and metallic aluminum sheets. The solid material (leaching residue), the outer aluminum structure, the graphite and the aluminum and copper sheets are subjected to an elutriation step in which water is fed from the bottom of the tank (or column) and aluminum and graphite exit from the top (overflow), while copper and the outer structure of the battery exit from the bottom of the tank (underflow). The separation of aluminum and graphite is carried out by sieving with a mesh smaller than 2 mm, and the separation of copper and the outer structure is also carried out by sieving with an opening smaller than 2 mm.

[0220] The leach liquor is subjected to manganese precipitation by ozone 110, which can be carried out in a batch reactor or in a column in a continuous system, using a gas flow rate between 0.2 L / min to 3.0 L / min, preferably between 0.6 L / min to 2 L / min, at a temperature range between 10 °C to 60 °C, preferably between 15 °C to 35 °C. After the reaction, solid-liquid separation is carried out by filtration using filters with a pore size of up to 2 pm, resulting in manganese oxide as a product, with an efficiency of up to 99%. This ozonation technique has not been explored in lithium battery recycling processes, as existing processes focus on the extraction of manganese through solvent techniques. The use of ozone has proven to be a viable selective technique for manganese separation in a single step, already in the form of an oxide, with a purity of at least 95%.

[0221] The filtrate (solution) from step 110 can be subjected to an aluminum precipitation step 111A using or at a pH range of 3.0 to 5.0, at a temperature between 25 °C to 80 °C and a reaction time of 0.5 to 3.0 hours, achieving an aluminum precipitation efficiency of up to 99%. Aluminum hydroxide, aluminum carbonate or aluminum oxide (the latter obtained after treatment between 200 °C to 800 °C for 1 to 5 hours) can be obtained. Another aluminum separation technique that can be carried out is electrodialysis 111B, as shown in Figure 2 , using cationic and anionic membranes, with a current between 200 mA and 400 mA for 30 hours. Then, the aluminum concentrated solution from electrodialysis 111B is subjected to aluminum precipitation step 111A to obtain aluminum hydroxide, aluminum carbonate or aluminum oxide, as previously described. This step has an aluminum precipitation efficiency of up to 99%. The use of electrodialysis has proven to be an important alternative for continuous flow aluminum separation, especially without the addition of reagents. This technique is widely used for water desalination, but has been found to be effective also for aluminum separation in hydrometallurgical processes.

[0222] After the separation of aluminum by filtration using 2 pm filter, the solution is subjected to cobalt separation. Cobalt separation is carried out by using hypophosphorous acid solvent extraction, where lithium and nickel are retained in the aqueous phase and cobalt is retained in the organic phase. Stripping step is important to transfer the extracted cobalt from the organic phase back to the aqueous phase, which is then subjected to precipitation step 113 and precipitation step 114, where cobalt oxalate, cobalt hydroxide, cobalt carbonate or metallic cobalt (by electrolysis) can be obtained. Cobalt solvent extraction step 112A is carried out using hypophosphorous acid in counter current using a ratio of aqueous phase to organic phase between 1 :5 to 5:1, using a concentration of hypophosphorous acid between 5% to 25% v / v at a temperature range of 25°C to 60°C. In the solvent extraction step, using single contact, cobalt recovery can be as high as 99%. In step 112A, the organic phase can be treated with sulfuric acid in counter current using a ratio of aqueous phase to organic phase between 1 :5 to 5:1, using a concentration of sulfuric acid between 0.1 mol / L to 5.0 mol / L at a temperature between 25°C to 60°C to obtain a solution of cobalt sulfate. This solution can be subjected to crystallization to obtain crystallized cobalt sulfate. The precipitation can be carried out using sodium oxalate ( ) or oxalic acid ( ) in a stoichiometric amount to 20% excess to obtain cobalt oxalate (1 :1 ratio) followed by calcination to produce cobalt oxide. Alternatively, cobalt carbonate can be obtained by precipitation at a temperature between 25°C to 80°C, using , at a pH of 6 to 10 for 30 minutes to 3.0 hours. Filtration is carried out using 2 pm filter to retain the solid phase (cobalt product / salt).

[0223] Nickel precipitation step 113 after cobalt separation can be carried out using or at a temperature between 25°C to 80°C and a pH range of 5.0 to 9.0 for a duration of 0.5 to 3.0 hours. In this step, nickel hydroxide, nickel carbonate or nickel oxide (the latter is obtained after treatment between 200°C to 800°C for 1.0 to 5.0 hours) can be produced. After the reaction, nickel recovery is as high as 99% by filtration using 2 pm filter to obtain the solid.

[0224] The battery recycling process 100 of the present invention ends with precipitation step 114 of the remaining lithium, which can be carried out by one of the following methods:

[0225] i) crystallization of the solution resulting from nickel precipitation step 113 to obtain lithium sulfate ( ) at a temperature between 80°C to 110°C using a reaction time between 1.0 to 5.0 hours;

[0226] ii) adding sodium phosphate (solid or in solution) to the solution at a temperature between 25°C and 90°C with a reaction time between 1.0 and 5.0 hours under stirring to obtain lithium phosphate ( ) at a concentration between 50 g / L and 200 g / L;

[0227] iii) adding sodium carbonate to the solution at a temperature between 25°C and 90°C with a reaction time between 1.0 and 5.0 hours at a concentration between 50 g / L and 200 g / L under stirring to obtain lithium carbonate ( ) at a concentration between 0.2 g / L and 1.0 g / L;

[0228] iv) adding calcium hydroxide to the lithium carbonate obtained in (iii) at a temperature between 25°C and 90°C with a reaction time between 1.0 and 5.0 hours at a concentration between 0.2 g / L and 1.0 g / L to obtain lithium hydroxide ( ).

[0229] At the end of the method 100, after the step 114 of precipitating the remaining lithium, the solution can undergo a crystallization step to obtain sodium sulfate crystals as a by-product and the acid used in the leaching is recovered for reuse in the leaching step.

[0230] Figure 3 and Figure 4 Figure illustrates another alternative embodiment of the battery recycling method 100 of the present application, wherein the ozonation step 110 for manganese separation is not present, as manganese can be separated together with cobalt in the solvent extraction step 112B. The battery discharging step 101, the step 102 of disassembling and separating the components of the battery, the step 103 of grinding the battery cells, the step 104 of separating the plastic parts with graphite and active material, the step 105 of precipitating fluorine, the step 106 of precipitating lithium, the step 107 of leaching with acid, the step 108 of filtering the leaching solution, the step 109 of separating the solid materials, the step 111A of precipitating aluminum, the step 113 of precipitating nickel and the step 114 of precipitating the remaining lithium are preserved in this embodiment of the present application.

[0231] The technique of separating aluminum by electrodialysis 111B is also proven suitable for this embodiment of the present application, using cationic and anionic membranes, with a current in the range of 200 mA to 400 mA for 30 hours. The leachate from the filtration step 108 of the leaching solution undergoes the electrodialysis separation step 111B, and the concentrated aluminum solution obtained from the electrodialysis 111B undergoes the aluminum precipitation step 111A to obtain aluminum hydroxide, aluminum carbonate or aluminum oxide, as previously described. This step reaches up to 99% efficiency in aluminum precipitation. Then, the concentrated cobalt, manganese, nickel and lithium solution resulting from the electrodialysis 111B is directed to the cobalt and manganese solvent extraction step 112B. Figure 5The cobalt and manganese extraction step 112B and its six sub-steps are illustrated:

[0232] - 112B.1 ) extraction of cobalt and manganese from solution using a phosphine such as bis(2,4,4-trimethylpentyl) phosphinic acid, di-(2-ethylhexyl) phosphonic acid, trialkyl phosphine, phosphonic acid or phosphinic acid, producing two phases, an aqueous phase and an organic phase, the aqueous phase being discharged; stripping of cobalt and manganese from the organic phase from sub-step 112B.1 ), wherein cobalt is extracted in the form of cobalt sulphate in an aqueous phase and manganese is extracted in the form of manganese sulphate in an aqueous phase;

[0233] - 112B.3) extraction of manganese from the solution resulting from sub-step 112B.2) using a phosphine such as bis(2,4,4-trimethylpentyl) phosphinic acid, di-(2-ethylhexyl) phosphonic acid, trialkyl phosphine, phosphonic acid or phosphinic acid, producing two phases: an aqueous phase containing cobalt and an organic phase containing manganese, the aqueous phase containing cobalt being directed to cobalt precipitation;

[0234] - 112B.4) precipitation of cobalt from the aqueous phase from sub-step 112B.3) using a reagent stripping of manganese from the organic phase solution from sub-step 112B.3), wherein manganese is extracted in the form of manganese sulphate in an aqueous phase;

[0235] - 112B.5) precipitation of manganese from the aqueous phase from sub-step 112B.4) using a reagent , , or wherein manganese is precipitated in the form of manganese hydroxide, manganese oxalate or manganese carbonate and is removed from solution by filtration using a filter with a pore size in the range of 0.1 to 4 pm; and

[0236] - 112B.6) precipitation of cobalt from the aqueous phase of the solution in sub-step 112B.3) using a reagent , oxalic acid, sodium oxalate or wherein cobalt is precipitated in the form of cobalt hydroxide, cobalt oxalate or cobalt carbonate and is removed from solution by filtration using a filter with a pore size in the range of 0.1 to 4 pm.

[0237] Extraction sub-steps 112B.1 and 112B.3 can be performed in counter-current fashion at a temperature ranging between 25°C and 60°C, with a ratio between the aqueous phase and the organic phase ranging between 1 :5 and 5:1 and a concentration of phosphinic acid ranging between 5% and 25% v / v. Strip sub-steps 112B.2 and 112B.4 can be performed in counter-current fashion at a temperature ranging between 25°C and 60°C, with a ratio between the aqueous phase and the organic phase ranging between 1 :5 and 5:1 and a concentration of manganese ranging between 0.1 mol / L and 5.0 mol / L. Manganese precipitation sub-step 112B.5 and cobalt precipitation sub-step 112B.6 can be performed at a pH ranging between 6.0 and 10.0, a reaction time ranging between 0.5 and 3.0 hours and a temperature ranging between 25°C and 80°C, with the reagents added in an amount ranging from the stoichiometric amount to an excess of 20%.

[0238] Optionally, the manganese oxalate obtained in sub-step 112B.4 and the cobalt oxalate obtained in sub-step 112B.6 can undergo a calcination step at a temperature ranging between 400°C and 800°C to obtain cobalt oxide and manganese oxide.

[0239] With the present application, the resynthesis of cathodes can be performed. Resynthesis consists of the production / synthesis of active materials from lithium-ion batteries. Such active materials refer to the cathodes of the batteries. The term "resynthesis" is used to define the synthesis of active materials, such as LCO ), NCA ), LMO or ), NMC ) and LMO-NMC, from the leaching solution produced during the leaching of lithium-ion batteries immediately after the leaching step 107, as described hereinafter:

[0240] - NMC cathode: removal of aluminium by precipitation 110A or electrodialysis 110B;

[0241] - NCA cathode: precipitation of manganese by ozonation 110;

[0242] - LMO cathode: use of the manganese oxide obtained in step 110 (ozonation or solvent extraction) with the lithium solution obtained after the nickel precipitation step 113;

[0243] - LCO cathode: use of the cobalt sulfate solution with the lithium solution obtained after the nickel precipitation step 113.

[0244] Alternatively, the products obtained in the separation step, extraction step and precipitation step 110, 111A, 111B, 112A, 112B, 113 and 114 can be used for indirect resynthesis instead of direct resynthesis from the leach liquor. The indirect resynthesis process can be carried out by co-precipitation with and calcination in an inert, air or oxygen atmosphere at a temperature between 600 and 800 °C for a reaction time between 0.5 and 12 hours.

[0245] The main innovation of the present application is the absence of a reducing agent in the leaching step 107 and the mechanical processing without any thermal treatment to concentrate the metal of interest from the cathode of the battery. Moreover, due to the presence of metallic aluminum from the current collector sheet, the leaching step can achieve efficiency values close to 99% for Ni, Co, Mn and Li. This was confirmed for all the batteries studied using inorganic acids (sulfuric and phosphoric) and organic acids (citric acid). The flexibility was evaluated by performing leaching experiments on batteries separately and then by mixing different types of cathodes such as for example NCA and NMC and the leaching efficiency achieved was at least 95%.

[0246] An acid wash step (pH 5.0) was performed on the solid product obtained from the aluminum precipitation step 111A to remove the co-precipitated metals.

[0247] Another metal separation technique that can be performed after the acid leaching and filtration step is the separation technique using ozonation and electrodialysis as in Figure 6The formed liquid (containing lithium, nickel, cobalt, manganese and aluminium) is subjected to an ozonation step 118. In this step, manganese is recovered and the resulting solution (containing lithium, nickel, cobalt and aluminium) is subjected to electrodialysis separation steps 119-121. The first electrodialysis step 119 uses a monovalent membrane to separate lithium from the other metals in the concentrated solution obtained from leaching. The second electrodialysis step 120 uses the cationic membrane in a system with both cationic and anionic membranes to separate nickel. This step requires the preparation of the solution before passing through the membrane. The solution containing nickel, cobalt and aluminium is complexed by the addition of EDTA. After passing through the cationic membrane in the anion-cation membrane system, nickel is separated. The solution containing cobalt and aluminium is subjected to the third and final electrodialysis step 121. Before this, the solution must be prepared by the addition of the complexing agent 1-hydroxyethane-1,1-diphosphonic acid. After complexation, the solution passes through the cationic membrane in the cation-anion membrane system, allowing the separation of cobalt and aluminium into two different solutions. After all the separation steps, each solution containing a specific metal is subjected to a recovery step, which can be precipitation or electrodeposition.

[0248] The leachate is treated by ozonation 118 for manganese separation. The ozonation method consists of injecting ozone into the leachate leaving the leaching step to increase the redox potential of the solution and precipitate manganese. The ozone is generated from a generator and oxygen, which is then injected directly into the solution to react with manganese ions. After the ozonation treatment of the leachate, manganese is separated in the form of oxidized manganese by filtration using filters with a pore size in the range of 0.1 to 4 pm, or by electrodeposition (also in the form of an oxide).

[0249] The use of electrodialysis proved to be an important alternative for metal separation in continuous flow, especially without the addition of reagents. Although this technique is widely used for water desalination, it was found to be effective also for metal separation in hydrometallurgical processes.

[0250] After ozonation, a lithium separation step is performed on the solution exiting the ozonation treatment by using monovalent membrane electrodialysis 119, wherein the electrodialysis is performed at a current ranging from 10 mA to 400 mA, preferably from 10 mA to 70 mA, with a current density of 1.0 mA / cm2to 31.25 mA / cm2, preferably from 12.5 mA / cm2to 25 mA / cm2, and a reaction time of 20 hours to 160 hours, preferably up to 30 hours. The lithium concentrated solution is then subjected to a lithium recovery step by precipitation, while the remaining solution is directed to a new electrodialysis step. Next, the solution exiting the lithium separation step is complexed with ethylenediaminetetraacetic acid (EDTA) by electrodialysis, followed by a nickel separation step 120 by electrodialysis using the cationic membrane in a system comprising both cationic and anionic membranes. The electrodialysis is performed at a current ranging from 100 mA to 500 mA, preferably from 200 mA to 400 mA, with a current density of between 1.0 mA / cm2to 31.25 mA / cm2, preferably between 12.5 mA / cm2to 25 mA / cm2, and a reaction time of 20 to 160 hours, preferably up to 30 hours. The nickel concentrated solution is then subjected to a recovery step by precipitation or electrodeposition of nickel (in metallic form), while the remaining solution is sent to another electrodialysis step. Finally, the solution exiting the nickel separation step is complexed with 1-hydroxyethane-1,1-diphosphonic acid (HEDP) by electrodialysis, and subsequently subjected to a cobalt and aluminum separation step 121 by electrodialysis using the cationic membrane in a system comprising both cationic and anionic membranes. The electrodialysis is performed at a current ranging from 100 mA to 500 mA, preferably from 200 mA to 400 mA, with a current density of between 1.0 mA / cm2to 31.25 mA / cm2, preferably between 12.5 mA / cm2to 25 mA / cm2, and a reaction time of 20 to 160 hours, preferably up to 30 hours. This step produces two different solutions, which are subjected to recovery steps by precipitation or electrodeposition of cobalt (in metallic form) and precipitation or electrodeposition of aluminum (in metallic form).

[0251] As indicated, after all the electrodialysis separation steps, each solution containing a specific metal is subjected to a recovery step, which can be precipitation or electrodeposition. Precipitation occurs as discussed previously, while electrodeposition also occurs as described previously.

[0252] As in the previous example, the solutions containing the metals are subjected to recovery steps by precipitation or electrodeposition, as discussed previously. Figure 6The metal separation techniques shown, following the acid leaching step and separation by ozonation and electrodialysis, present three related aspects: a) applying a solution with high metal concentration (leaching solution) to ozonation technology and manganese recovery; b) applying a solution with high metal concentration (leaching solution) to the electrodialysis technology in the first step, i.e. lithium separation using a monovalent membrane; and c) separating cobalt and aluminum using the complexing agent HEDP.

[0253] Another metal separation technique performed after acid leaching and separation steps is... Figure 7 The electrodialysis technique is shown in the figure. The resulting liquid (containing lithium, nickel, cobalt, manganese, and aluminum) undergoes a first electrodialysis stage 122. In this stage, a monovalent membrane is used to separate lithium from other metals present in the concentrated leachate solution. A second electrodialysis stage 123 involves separating nickel using a cation exchange membrane in a system of cation and anion exchange membranes. This nickel separation requires solution preparation before passing through the membrane. The solution containing nickel, cobalt, manganese, and aluminum is complexed by adding EDTA. After the solution passes through the cation exchange membrane in the cation and anion exchange membrane system, nickel is separated, producing a single-element nickel solution. The solution containing manganese, cobalt, and aluminum undergoes a third electrodialysis stage 124. Prior to this, a solution containing manganese, cobalt, and aluminum needs to be prepared by adding the complexing agent EDTA. After complexation, the solution passes through the cation exchange membrane in the cation and anion exchange membrane system, thereby achieving the separation of manganese from other metals (cobalt and aluminum). The solution containing cobalt and aluminum undergoes a fourth and final electrodialysis stage 125. Before this, a solution containing cobalt and aluminum must be prepared by adding the complexing agent HEDP. Following complexation, the solution passes through the cation membrane in the system of cation and anion membranes, resulting in the separation of cobalt and aluminum into two distinct solutions. After all separation stages, each solution containing the specific metal undergoes a recovery step, which may include precipitation or electrodeposition.

[0254] Electrodialysis has proven to be an important alternative for continuous flow metal separation, especially without the addition of reagents. This technique is widely used in water desalination, but it has also been found to be effective for metal separation in hydrometallurgical processes.

[0255] The leachate is subjected to a lithium separation step 122 by electrodialysis using monovalent membranes, wherein the electrodialysis is performed at a current ranging from 10 to 400 mA, preferably from 10 to 70 mA, with a current density of 0.1 mA / cm2to 25 mA / cm2, preferably from 12.5 mA / cm2to 25 mA / cm2, and a reaction time of between 20 and 160 hours, preferably up to 30 hours. The lithium concentrated solution is subjected to a lithium recovery step by precipitation, while the remaining solution is subjected to a subsequent electrodialysis step. Next, the solution leaving the lithium separation step is subjected to complexation with ethylenediaminetetraacetic acid (EDTA) by electrodialysis, followed by a nickel separation step by electrodialysis using the cationic membranes in a system of cationic and anionic membranes. The electrodialysis is performed at a current ranging from 100 mA to 500 mA, preferably from 200 mA to 400 mA, with a current density of 0.1 mA / cm2to 25 mA / cm2, preferably from 12.5 mA / cm2to 25 mA / cm2, and a reaction time of between 20 and 160 hours, preferably up to 30 hours. The nickel concentrated solution is subjected to a recovery step by precipitation or electrodeposition of nickel (in metallic form), while the remaining solution is subjected to a subsequent electrodialysis step. The solution leaving the nickel separation step is subjected to complexation with ethylenediaminetetraacetic acid (EDTA) by electrodialysis, followed by a manganese separation step by electrodialysis using the cationic membranes in a system of cationic and anionic membranes. The electrodialysis is performed at a current ranging from 100 mA to 500 mA, preferably from 200 mA to 400 mA, with a current density of 0.1 mA / cm2to 25 mA / cm2, preferably from 12.5 mA / cm2to 25 mA / cm2, and a reaction time of between 20 and 160 hours, preferably up to 30 hours. The manganese concentrated solution is subjected to a recovery step by precipitation or electrodeposition of manganese (in oxide form), while the remaining solution is subjected to a subsequent electrodialysis step. The solution leaving the manganese separation step is subjected to complexation with 1-hydroxyethane-1,1-diphosphonic acid (HEDP) by electrodialysis, followed by a cobalt and aluminum separation step by electrodialysis using the cationic membranes in a system of cationic and anionic membranes. The electrodialysis is performed at a current ranging from 100 mA to 500 mA, preferably from 200 mA to 400 mA, with a current density of 0.1 mA / cm2to 25 mA / cm2, preferably from 12.5 mA / cm2to 25 mA / cm2, and a reaction time of between 20 and 160 hours, preferably up to 30 hours. Two different solutions are obtained, which are subjected to a recovery step by precipitation or electrodeposition of cobalt (in metallic form) and precipitation or electrodeposition of aluminum (in metallic form), respectively.

[0256] As indicated, after all the electrodialysis separation steps, each solution containing a specific metal is subjected to a recovery step, which can be precipitation or electrodeposition. Precipitation occurs as previously discussed, electrodeposition also occurs as previously discussed.

[0257] Figure 7 The metal separation technique that can be carried out by electrodialysis after the acid leaching and filtration steps, illustrated in the middle, presents two relevant aspects: a) the application of solutions with high metal concentration to the electrodialysis technique in the first step, i.e., the separation of lithium using monovalent membranes; and b) the separation of cobalt and aluminum using the complexing agent HEDP.

[0258] The new battery recycling process (100) of the present invention has a combination of advantages, the following being highlighted in particular:

[0259] - the possibility of recycling various types of batteries (active materials / cathodes and construction) in a flexible way;

[0260] - discharging the batteries without loss of material;

[0261] - there is no thermal treatment step in the mechanical and chemical processing of the batteries to be recycled;

[0262] - grinding the batteries in water;

[0263] - there is no consumption of reducing agents in the leaching step;

[0264] - obtaining a high-purity product derived from the active cathode material of the batteries;

[0265] - the possibility of re-synthesizing cathodes from the leaching solutions or products obtained from the recycling process;

[0266] - the recovery of plastics, metallic copper, metallic aluminum and the external battery structure by physical separation during the recycling of the batteries;

[0267] - alternative methods of metal separation after leaching, such as the use of ozone and membranes (electrodialysis).

[0268] This written description uses examples to explain the invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the invention is defined by the claims, and can include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Claims

1. A battery recycling method (100), characterized in that, The battery recycling method (100) includes the following steps: Discharge the battery to be recycled (101). Disassemble and separate the components (102) of the battery, wherein the components are grouped into: electronic parts and protective structures, and battery cells; The battery cell (103) is ground, wherein the grinding is performed in a cooling fluid; Plastic parts (104) containing graphite and active material are separated from the ground material derived from the grinding step (103), wherein the plastic parts containing the graphite and active material are washed and sieved (115) to separate the graphite and active material, the graphite and active material are leached, and the sieve used has a mesh size between 0.1 and 4 mm; join in or Fluorine is precipitated from the solution derived from the separation step (104) (105), wherein the precipitated fluorine is removed from the solution by filtration (116) using a filter with a pore size in the range of 0.1 to 4 µm; By joining Lithium is precipitated from the solution derived from the fluorine precipitation step (105) (106), wherein the precipitated lithium is removed from the solution by filtration (117) using a filter with a pore size in the range of 0.1 to 4 µm; Leaching with acid or the solid obtained from the grinding and physical separation steps; The leachate solution (108) was filtered using a filter with a pore size in the range of 0.1 to 4 µm to separate the leachate and solid material; Separate the solid material (109) filtered out in step (108); The leachate from the output of step (108) is treated by ozonation (110) to separate manganese, and the manganese is separated in the form of manganese oxide by filtration using a filter with a pore size of 0.1 to 4 µm. By joining or Aluminum is precipitated from the solution obtained by the ozonation step (110) (111A), wherein the aluminum is precipitated in the form of aluminum oxide, aluminum hydroxide or aluminum carbonate, and the aluminum is removed from the solution by filtration using a filter with a pore size in the range of 0.1 to 4 µm; Cobalt is extracted from the solution obtained by the aluminum precipitation step (111A) in three sub-steps by solvent extraction (112A): a) Using phosphonates such as bis(2,4,4-trimethylpentyl)phosphonic acid, di-(2-ethylhexyl)phosphoric acid, trialkylphosphine, phosphonic acid, or phosphonic acid as extractants to produce two phases, an aqueous phase and an organic phase. b) Discharge the aqueous phase, and c) The organic phase is fed into a container with In the back-extraction solution, cobalt is extracted in the form of cobalt sulfate, and then the cobalt is removed from the solution by filtration using a filter with a pore size in the range of 0.1 to 4 µm; By joining or Nickel is precipitated (113) from the solution obtained by the cobalt solvent extraction step (112A), wherein the nickel is precipitated as nickel oxide, nickel hydroxide, or nickel carbonate, and the nickel is removed from the solution by filtration using a filter with a pore size in the range of 0.1 to 4 µm; and Residual lithium is precipitated from the solution obtained by the nickel precipitation step (113) (114), wherein the residual lithium is used as... , , or The lithium is precipitated in the form of a precipitate and the remaining lithium is removed from the solution by filtration using a filter with a pore size in the range of 0.1 to 4 µm.

2. The battery recycling method (100) according to claim 1, characterized in that: The method is applicable to LCO, NCA, NMC (111, 622, 532, 631, 811), LMO and LMO-NMC batteries of square, cylindrical and pouch types.

3. The battery recycling method (100) according to claim 1 or 2, characterized in that: The discharge step (101) is carried out in two discharge steps, which makes it possible to recover electrical energy discharged from the battery.

4. The battery recycling method (100) according to any one of claims 1 to 3, characterized in that: The discharge step (101) is performed by a resistor.

5. The battery recycling method (100) according to any one of claims 1 to 4, characterized in that: The grinding step (102) is performed using a shredder-type grinder or a blade-type grinder.

6. The battery recycling method (100) according to any one of claims 1 to 5, characterized in that: The grinding step (102) includes continuously adding cooling fluid, feeding the battery cell into the grinder at intervals of 1 to 20 seconds between each part, and the ground material having a particle size of less than 50 mm.

7. The battery recycling method (100) according to any one of claims 1 to 6, characterized in that: The cooling fluid used in the grinding step (102) is water.

8. The battery recycling method (100) according to any one of claims 1 to 7, characterized in that: The separation step (104) is performed by at least one of the following methods: decantation, centrifugation, or shaking table.

9. The battery recycling method (100) according to any one of claims 1 to 8, characterized in that: The sieve used in the separation step (104) has a mesh size between 1 and 2 mm.

10. The battery recycling method (100) according to any one of claims 1 to 9, characterized in that: In the fluorine precipitation step (105), the fluorine is added at a temperature between 25°C and 90°C for a reaction time of up to 2.0 hours. or The amount is between stoichiometric and 20% excess.

11. The battery recycling method (100) according to any one of claims 1 to 10, characterized in that: In the lithium precipitation step (106), using a reaction time of up to 2.0 hours, at a temperature between 20°C and 80°C, and with a lithium precipitation yield of 10%, the added... The amount is between stoichiometric and 20% excess.

12. The battery recycling method (100) according to any one of claims 1 to 11, characterized in that: The acid used in the leaching step (107) is selected from sulfuric acid, phosphoric acid or citric acid.

13. The battery recycling method (100) according to any one of claims 1 to 12, characterized in that: The leaching step (107) is carried out in the absence of a reducing agent.

14. The battery recycling method (100) according to any one of claims 1 to 13, characterized in that: The leaching step (107) has an acid concentration in the range of 0.5 mol / L to 4.0 mol / L, preferably in the range of 0.7 mol / L to 2 mol / L, a temperature between 25°C and 90°C, preferably between 60°C and 90°C, and a reaction time between 0.5 and 5.0 hours, preferably between 1 and 3 hours.

15. The battery recycling method (100) according to any one of claims 1 to 14, characterized in that: The solid materials filtered out in the filtration step (108) of the leaching solution include graphite, residues of the external structure of the battery, copper sheets, and aluminum sheets.

16. The battery recycling method (100) according to any one of claims 1 to 15, characterized in that: The separation step (109) is carried out by at least one of the following methods: decantation, centrifugation, vibrating table, sieving and washing.

17. The battery recycling method (100) according to any one of claims 1 to 16, characterized in that: The sieve used in the sieving of the separation step (109) has a mesh size between 0.03 and 4.0 mm.

18. The battery recycling method (100) according to any one of claims 1 to 17, characterized in that: The sieve used in the sieving of the separation step (109) has a mesh size between 1.5 and 3.0 mm.

19. The battery recycling method (100) according to any one of claims 1 to 18, characterized in that: The separation step (109) is performed in a conventional analyzer.

20. The battery recycling method (100) according to any one of claims 1 to 19, characterized in that: The ozonation step (110) consists of injecting ozone directly into the leachate leaving step (108) to react with manganese ions. The ozone is generated by a generator and oxygen. Step (110) is carried out in a column in a batch reactor or continuous system at a temperature between 10°C and 60°C, preferably between 15°C and 35°C, using an ozone gas flow rate between 0.2 L / min and 3 L / min, preferably between 0.6 L / min and 2 L / min.

21. The battery recycling method (100) according to any one of claims 1 to 20, characterized in that: The aluminum precipitation step (111A) is carried out at a pH range of 3.0 to 5.0, a temperature range of 25°C to 80°C, and a reaction time range of 0.5 to 3.0 hours.

22. The battery recycling method (100) according to any one of claims 1 to 21, characterized in that: The cobalt solvent extraction step (112A) is carried out countercurrently using hypophosphino acid at a temperature between 25°C and 60°C, with an aqueous phase to organic phase ratio between 1:5 and 5:1, and a hypophosphino acid concentration between 5% and 25% v / v, to obtain a cobalt sulfate solution.

23. The battery recycling method (100) according to any one of claims 1 to 22, characterized in that: The nickel precipitation step (113) is carried out at a pH range of 5.0 to 9.0, a temperature range of 25°C to 80°C, and a reaction time range of 0.5 to 3.0 hours.

24. The battery recycling method (100) according to any one of claims 1 to 23, characterized in that: The remaining lithium precipitation step (114) is performed by one of the following methods: i) The solution obtained from the nickel precipitation step (113) is crystallized at a temperature between 80°C and 110°C for a reaction time between 1.0 and 5.0 hours to obtain lithium sulfate. ; ii) Sodium phosphate (solid or in solution) is added to the solution under stirring at a temperature between 25°C and 90°C for a reaction time between 1.0 and 5.0 hours to obtain lithium phosphate (… ); iii) Sodium carbonate is added to the solution under stirring at a temperature between 25°C and 90°C and a reaction time between 1.0 and 5.0 hours, at a concentration between 50 g / L and 200 g / L, to obtain lithium carbonate ( );or iv) Using a temperature between 25°C and 90°C and a reaction time between 1.0 and 5.0 hours, calcium hydroxide is added to the lithium carbonate obtained in section iii) at a concentration between 0.2 g / L and 1.0 g / L to obtain lithium hydroxide ( ).

25. The battery recycling method (100) according to any one of claims 1 to 24, characterized in that, The battery recycling method (100) further includes: The step (111B) involves separating aluminum from the solution by electrodialysis using a cation exchange membrane, wherein the electrodialysis is carried out in a current range of 200 mA to 400 mA and a reaction time of up to 30 hours, and wherein the aluminum concentrate solution undergoes the aluminum precipitation step (111A), while the remaining solution undergoes a step of extracting cobalt by solvent (112A).

26. The battery recycling method (100) according to any one of claims 1 to 25, characterized in that, The battery recycling method (100) further includes: Sodium oxalate in amounts between stoichiometric and 20% excess. ) or oxalic acid ( Add it to the cobalt sulfate solution obtained by solvent extraction of cobalt (112A) to obtain cobalt oxalate precipitate in a 1:1 molar ratio; Subsequently, the cobalt oxalate solution is subjected to a calcination step to obtain cobalt oxide, and optionally, the amount added is between stoichiometric and 20% excess, within a pH range of 6.0 to 10.0, a reaction time between 0.5 and 3.0 hours, and a temperature between 25°C and 80°C. To obtain cobalt carbonate; or The solution is subjected to electrolysis to obtain cobalt in metallic form. The cobalt oxide, cobalt carbonate, and metallic cobalt are removed from the solution by filtration using a filter with a pore size in the range of 0.1 to 4 μm.

27. The battery recycling method (100) according to any one of claims 1 to 26, characterized in that, The battery recycling method (100) further includes: In the filtration process for removing cobalt oxide, cobalt carbonate, and metallic cobalt from the solution, the filter used has a pore size in the range of 1 to 2 μm.

28. The battery recycling method (100) according to any one of claims 1 to 27, characterized in that: After the remaining lithium precipitation step (114), the solution undergoes a crystallization step to obtain sodium sulfate crystals, and the acid used in the leaching is recovered for reuse in the leaching step.

29. The battery recycling method (100) according to any one of claims 1 to 28, characterized in that: In the fluorine precipitation step (105), lithium precipitation step (106), leaching step (107), filtration step of the leaching solution (108), ozonation step (110), aluminum precipitation step (111A), cobalt solvent extraction step (112A), nickel precipitation step (113) and residual lithium precipitation step (114), the filters used have a pore size in the range of 1 to 2 μm.

30. The battery recycling method (100) according to any one of claims 1 to 29, characterized in that: The filters used are of the paper or membrane type.

31. A battery recycling method (100), characterized in that, The battery recycling method (100) includes the following steps: Discharge the battery to be recycled (101). Disassemble and separate the components (102) of the battery, wherein the components are grouped into: electronic parts and protective structures, and battery cells; The battery cell (103) is ground, wherein the grinding is performed in a coolant fluid; Plastic parts (104) containing graphite and active material are separated from the ground material obtained in the grinding step (103), wherein the plastic parts containing the graphite and active material are washed and sieved (115) to separate the graphite and active material, the graphite and active material are leached, and the sieve used has a mesh size between 0.1 and 4 mm; By joining or Fluorine is precipitated from the solution obtained in the separation step (104) (105), wherein the precipitated fluorine is removed from the solution by filtration (116) using a filter with a pore size in the range of 0.1 to 4 µm; By joining Lithium is precipitated from the solution obtained in the fluorine precipitation step (105) (106), wherein the precipitated lithium is removed from the solution by filtration (117) using a filter with a pore size in the range of 0.1 to 4 µm; The solids obtained from the grinding and physical separation steps are leached with acid; The leachate solution (108) was filtered using a filter with a pore size in the range of 0.1 to 4 µm to separate the leachate and solid material; Separate the solid material (109) filtered out in step (108); By joining or Aluminum (111A) is precipitated from the solution obtained in the leaching step (108), wherein the aluminum is precipitated in the form of aluminum oxide, aluminum hydroxide or aluminum carbonate, and the aluminum is removed from the solution by filtration using a filter with a pore size in the range of 0.1 to 4 µm; Cobalt and manganese are extracted from the solution obtained in the aluminum precipitation step (111A) by solvent extraction (112B) in six sub-steps: - 112B.1) Using phosphonates such as bis(2,4,4-trimethylpentyl)phosphonic acid, di-(2-ethylhexyl)phosphonic acid, trialkylphosphine, phosphonic acid, or phosphonates, cobalt and manganese are extracted from the solution, producing two phases—an aqueous phase and an organic phase—the aqueous phase is discharged. - 112B.2) Use Cobalt and manganese are back-extracted from the organic phase in sub-step 112B.1), wherein cobalt is extracted in the aqueous phase as cobalt sulfate and manganese is extracted in the aqueous phase as manganese sulfate. - 112B.3) Using phosphonates such as bis(2,4,4-trimethylpentyl)phosphonic acid, di-(2-ethylhexyl)phosphoric acid, trialkylphosphine, phosphonic acid, or phosphonic acid, manganese is extracted from the solution obtained in sub-step 112B.2), producing two phases: an aqueous phase containing cobalt and an organic phase containing manganese. The cobalt aqueous phase is directed to cobalt precipitation. - 112B.4) Utilization Manganese is back-extracted from the organic phase solution in sub-step 112B.3), wherein the manganese is extracted in the aqueous phase in the form of manganese sulfate. - 112B.5) Use of reagents , , or A reagent is used to precipitate manganese from the aqueous phase in sub-step 112B.4), wherein the manganese is precipitated as manganese hydroxide, manganese oxalate, or manganese carbonate, and the manganese is removed from the solution by filtration through a filter with a pore size in the range of 0.1 to 4 µm. - 112B.6) Using reagents , (oxalic acid), (Sodium oxalate) or One of the reagents precipitates cobalt from the aqueous phase of the solution in sub-step 112B.3), wherein the cobalt is precipitated in the form of cobalt hydroxide, cobalt oxalate or cobalt carbonate, and the cobalt is removed from the solution by filtration through a filter with a pore size in the range of 0.1 to 4 µm; By joining or Nickel is precipitated (113) from the solution obtained by the cobalt and manganese solvent extraction step (112B), wherein the nickel is precipitated as nickel oxide, nickel hydroxide, or nickel carbonate, and the nickel is removed from the solution by filtration through a filter with a pore size in the range of 0.1 to 4 µm; and Residual lithium is precipitated from the solution obtained by the nickel precipitation step (113) (114), wherein the residual lithium is used as... , , or The lithium is precipitated in the form of a precipitate and the remaining lithium is removed from the solution by filtration using a filter with a pore size in the range of 0.1 to 4 µm.

32. The battery recycling method (100) according to claim 31, characterized in that, The battery recycling method (100) further includes: The step of separating aluminum from the solution by electrodialysis using a cation exchange membrane (111B), wherein the electrodialysis is carried out in a current range of 200 mA to 400 mA and a reaction time of up to 30 hours, and wherein the aluminum concentrate solution undergoes the aluminum precipitation step (111A), while the remaining solution undergoes the cobalt and manganese solvent extraction step (112).

33. The battery recycling method (100) according to claim 31 or 32, characterized in that: The extraction sub-steps (112B.1) and (112B.3) are carried out countercurrently at a temperature range of 25°C to 60°C, using an aqueous phase to organic phase ratio between 1:5 and 5:1, and using a phosphonic acid concentration between 5% and 25% v / v. The back-extraction sub-steps (112B.2) and (112B.4) are performed at a temperature range of 25°C to 60°C, utilizing an aqueous phase to organic phase ratio between 1:5 and 5:1, and a concentration between 0.1 mol / L and 5.0 mol / L. Concentration occurs countercurrently, and The manganese precipitation sub-step (112B.5) and the cobalt precipitation sub-step (112B.6) are carried out in an amount of the reagents added in the range of stoichiometry to 20% excess, within a pH range of 6.0 to 10.0, a reaction time of 0.5 to 3.0 hours, and a temperature of 25°C to 80°C.

34. The battery recycling method (100) according to any one of claims 31 to 33, characterized in that: Manganese oxalate and cobalt oxalate undergo a calcination process at a temperature between 400°C and 800°C to obtain cobalt oxide and manganese oxide.

35. A battery recycling method (100), characterized in that, The battery recycling method (100) includes the following steps: Discharge the battery to be recycled (101). Disassembling and separating (102) the components of the battery, wherein the components are grouped into: electronic parts and protective structures, and battery cells; The battery cell (103) is ground, wherein the grinding is performed in a cooling fluid; Plastic parts (104) containing graphite and active material are separated from the ground material obtained by the grinding step (103), wherein the plastic parts containing the graphite and active material are washed and sieved (115) to separate the graphite and active material, the graphite and active material are leached, and the sieve used has a mesh size between 0.1 and 4 mm; By joining or Fluorine is precipitated from the solution obtained by separation step (104) (105), wherein the precipitated fluorine is removed from the solution by filtration (116) using a filter with a pore size between 0.1 and 4 µm; By joining Lithium is precipitated from the solution obtained by the fluorine precipitation step (105) (106), wherein the precipitated lithium is removed from the solution by filtration (117) using a filter with a pore size between 0.1 and 4 µm; The solid material obtained from the grinding and physical separation steps is leached with acid (107); The leachate solution (108) was filtered using a filter with a pore size in the range of 0.1 to 4 µm to separate the leachate and solid material; Separate the solid material (109) filtered out in step (108); Manganese is separated by treating the leachate from the output of the previous step by ozonation (118). A lithium separation step (119) is performed on the solution leaving the ozonation treatment by electrodialysis using a monovalent membrane, wherein the electrodialysis is performed in the current range of 10 to 400 mA, using a current density of 0.1 mA / cm² to 25 mA / cm² and a reaction time of 20 to 160 hours, wherein the lithium concentrate solution is subjected to a lithium recovery step, and the remaining solution is subjected to a subsequent electrodialysis step. The solution exiting the lithium separation step via electrodialysis is complexed with ethylenediaminetetraacetic acid (EDTA), and a nickel separation step (120) is subsequently performed by electrodialysis using a cation exchange membrane in a system with cation and anion exchange membranes, wherein the electrodialysis is carried out in the current range of 100 mA to 500 mA, using a current density of 1.0 mA / cm² to 31.25 mA / cm² and a reaction time of 20 to 160 hours; wherein the nickel concentrate solution undergoes a recovery step, and the remaining solution undergoes a subsequent electrodialysis step; and The solution exiting the nickel separation step via electrodialysis is complexed with 1-hydroxyethane-1,1-diphosphonic acid (HEDP), and then subjected to a cobalt and aluminum separation step (121) by electrodialysis using a cation exchange membrane in a system having both cation and anion exchange membranes, wherein the electrodialysis is carried out at a current density of 1.0 mA / cm² to 31.25 mA / cm² and a reaction time of 20 to 60 hours in the current range of 100 mA to 500 mA; and wherein two different solutions are obtained for cobalt and aluminum recovery steps.

36. A battery recycling method (100), characterized in that, The battery recycling method (100) includes the following steps: Discharge the battery to be recycled (101). Disassemble and separate the components (102) of the battery, wherein the components are grouped into: electronic parts and protective structures, and battery cells; The battery cell (103) is ground, wherein the grinding is performed in a cooling fluid; Plastic parts (104) containing graphite and active material are separated from the ground material obtained by the grinding step (103), wherein the plastic parts containing the graphite and active material are washed and sieved (115) to separate the graphite and active material, the graphite and active material are leached, and the sieve used has a mesh size between 0.1 and 4 mm; By joining or Fluorine is precipitated from the solution derived from the separation step (104) (105), wherein the precipitated fluorine is removed from the solution by filtration (116) using a filter with a pore size between 0.1 and 4 µm; By joining Lithium is precipitated from the solution derived from the fluorine precipitation step (105) (106), wherein the precipitated lithium is removed from the solution by filtration (117) using a filter with a pore size between 0.1 and 4 µm; The solids derived from the grinding and physical separation steps are leached with acid (107). The leachate solution (108) was filtered using a filter with a pore size in the range of 0.1 to 4 µm to separate the leachate and solid material; Separate the solid material (109) filtered out in step (108); The leachate from the previous step is subjected to a lithium separation step (122) by electrodialysis using a monovalent membrane, wherein the electrodialysis is carried out in the current range of 10 to 400 mA, using a current density of 0.1 mA / cm² to 25 mA / cm² and a reaction time of 20 to 160 hours, wherein the lithium concentrate solution is subjected to a lithium recovery step, and the remaining solution is subjected to a subsequent electrodialysis step. The solution exiting the lithium separation step via electrodialysis is complexed with ethylenediaminetetraacetic acid (EDTA), and then the solution is subjected to a nickel separation step (123) by electrodialysis using a cation membrane in a system having cation and anion membranes, wherein the electrodialysis is carried out in the current range of 100 mA to 500 mA, using a current density of 1.0 mA / cm² to 31.25 mA / cm² and a reaction time of 20 to 160 hours, wherein the nickel concentrate solution undergoes a nickel recovery step, and the remaining solution undergoes a subsequent electrodialysis step; The solution exiting the nickel separation step via electrodialysis is complexed with ethylenediaminetetraacetic acid (EDTA), and then a manganese separation step (124) is performed by electrodialysis using a cation exchange membrane in a system having both cation and anion exchange membranes. The electrodialysis is carried out at a current density of 1.0 mA / cm² to 31.25 mA / cm² and a reaction time of 20 to 160 hours in the current range of 100 mA to 500 mA, wherein the manganese concentrate undergoes a manganese recovery step, and the remaining solution undergoes a subsequent electrodialysis step; and The solution exiting the manganese separation step via electrodialysis is complexed with 1-hydroxyethane-1,1-diphosphonic acid (HEDP), and then the solution is subjected to a cobalt and aluminum separation step (125) by electrodialysis using a cation membrane in a system having cation and anion membranes, wherein the electrodialysis is carried out in the current range of 100 mA to 500 mA, using a current density of 1.0 mA / cm² to 31.25 mA / cm² and a reaction time of 20 to 160 hours, and wherein two different solutions are obtained, the two different solutions being subjected to cobalt and aluminum recovery steps.

37. The battery recycling method (100) according to claim 35 or 36, characterized in that: The battery recycling method (100) includes the features defined in any one of claims 2 to 19.

38. The battery recycling method (100) according to claim 35 or 37, characterized in that: Manganese can be separated in the form of manganese oxide by filtration using a filter with a pore size between 0.1 and 4 µm, or by precipitation using a precipitant such as sodium hypochlorite, or by electrodeposition; and / or Lithium recovery occurs through precipitation; and / or Nickel recovery occurs through precipitation or electrodeposition; and / or Cobalt recovery occurs through precipitation or electrodeposition; and / or Aluminum recycling occurs through precipitation or electrodeposition.

39. The battery recycling method (100) according to claim 36 or 37, characterized in that: Manganese can be separated by ozone precipitation, which can occur in a batch reactor or in a column in a continuous system, at a temperature range of 10°C to 60°C, preferably 15°C to 35°C, at an ozone gas flow rate of 0.2 L / min to 4.0 L / min, preferably 0.6 L / min to 2 L / min, producing... Precipitate; or manganese can be separated by electrodeposition; and / or Lithium recovery occurs through precipitation; and / or Nickel recovery occurs through precipitation or electrodeposition; and / or Cobalt recovery occurs through precipitation or electrodeposition; and / or Aluminum recycling occurs through precipitation or electrodeposition.

40. The battery recycling method (100) according to claim 35, 37 or 38, characterized in that: The ozonation step consists of injecting ozone directly into the leachate from the leaching outlet to react with manganese ions. The ozone is generated by a generator and oxygen. The step is carried out in a batch reactor or in a column in a continuous system at an ozone gas flow rate of 0.2 L / min to 3 L / min, preferably 0.6 L / min to 2 L / min, and at a temperature between 10°C and 60°C.

41. The battery recycling method (100) according to any one of claims 35 to 40, characterized in that: Lithium precipitation , , or The lithium precipitate is formed in the form of a filter and is removed from the solution by filtration using a filter with a pore size in the range of 0.1 to 4 µm.

42. The battery recycling method (100) according to any one of claims 35 to 41, characterized in that: The lithium precipitation step is performed by one of the following methods: i) The solution is crystallized at a temperature between 80°C and 110°C for a reaction time between 1.0 and 5.0 hours to obtain lithium sulfate ( ); ii) Sodium phosphate (solid or in solution) is added to the solution under stirring at a temperature between 25°C and 90°C for a reaction time between 1.0 and 5.0 hours to obtain lithium phosphate (… ); iii) Sodium carbonate is added to the solution under stirring at a temperature between 25°C and 90°C, a reaction time between 1.0 and 5.0 hours, and a concentration between 50 g / L and 200 g / L, to obtain lithium carbonate ( ). );or iv) Calcium hydroxide is added to the lithium carbonate obtained in iii) at a concentration between 0.2 g / L and 1.0 g / L, using a temperature between 25°C and 90°C and a reaction time between 1.0 and 5.0 hours, to obtain lithium hydroxide ( ).

43. The battery recycling method (100) according to any one of claims 35 to 42, characterized in that: Following the lithium precipitation step, the solution undergoes a crystallization step to obtain sodium sulfate crystals, and the acid used in the leaching step is recovered for reuse in the leaching step.

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