METALS FROM SPENT LITHIUM-ION BATTERIES

FIELD OF THE INVENTION

[Para 1 ] The present invention relates to an improved method for recovering valuable metals from used lithium-ion, (hereunder Li-ion), batteries. More specifically, the invention provides a method for recovering cobalt and lithium together with other valuable metals.

BACKGROUND OF THE INVENTION AND PRIOR ART

[Para 2] Li-ion batteries are rechargeable batteries used to store and supply electrical power for many products such as vehicles, computers, telephones, and any other product empowered by Li-ion batteries.

[Para 3] Li-ion batteries include at least one Li-ion cell that includes an electrode. The electrode includes:

- one or more sheets of positive electrode (including intercalating lithium positive active material on the backing sheet) with a positive contact;

- one or more sheets of negative electrodes (usually negative active material with lithium intercalation on the support sheet) with a negative contact;

- a separator (typically a sheet of microporous polyolefin), electrically separating any two electrodes; - an electrical separator, (may be a sheet of microporous polyolefin), constituting a conductive separation between any two electrodes.

[Para 4] The positive active material may comprise metal oxides such as Li, Co, Ni, Mn. The negative active material may comprise metals (copper foil) and Li cations. The support sheets are usually metal foils, such as aluminum and copper. The contacts are usually made of a metal such as nickel-plated steel.

[Para 5] The electrode, flat or rolled, is located inside a cell housing. A cell housing is typically made of metal (e.g., steel), plastic or foil. One or more cells make up a single Li-ion battery.

[Para 6] A Li-ion battery may include an electrolyte, (e.g., LiPFe) in a solvent such as fluorinated alcohol (CnFn + 2OH), to provide a conductive separation between any two electrodes.

[Para 7] In one particularly common Li-ion battery, a plastic, aluminum, or steel battery case contains a plurality of cylindrical Li-ion cells and optionally monitoring electronics.

[Para 8] Each cylindrical Li-ion cell, (sometimes called finger cells), includes a cylindrical iron-containing (e.g., steel) casing that also serves as one of the two contacts in which is held a rolled-up electrode (sometimes called a jelly roll). The iron-containing casing is entirely or almost entirely covered with an insulating coating such as paint or plastic films.

[Para 9] Some of the metals in an electrode of a Li-ion cell are toxic and/or valuable. In addition, the presence of an alcohol-containing electrolyte in the composition of a cylindrical cell is inflammable and may cause an explosive situation if the tightness of such cell in air is violated. Therefore, it is beneficial to have an environmentally friendly and efficient method for recycling batteries containing Li-ion cells in order to recover valuable metals. For example, to prevent pollution of the environment with toxic transition metal oxides and to allow the reuse of these valuable metals in industry.

[Para 10] Recycling of batteries is becoming more and more important due to the increase in the number of used up batteries. Consequently, there is quite a lot of prior art on this subject.

[Para 1 1 ] Most of the prior art documents disclose dismantling the battery and converting it into powder form, through crushing, disassembling, dipping in alkali solution, sieving, washing, and pulverizing, before immersing into acids for recovery process.

[Para 12] It is known in the prior art to break or cut open the iron-containing housing and then to manually separate the electrodes from the casing remnants. Li-ion battery remnants are sometimes pre-crushed to prepare electrode material for hydrometallurgical processing. Since the electrolyte in Li-ion cells is toxic, corrosive and inflammable, complex and expensive methods are required to safely break or cut open the steel casing to access the electrodes and then to safely manipulate a separated electrode for further processing. [Para 1 3] Other documents disclose the use of dilute acid instead of concentrated acids for leaching action along with sulphate and carbonate containing compounds as precipitating agents for the conversion.

[Para 14] Other documents disclose the use of mineral acid along with H2O2 as a reductant of Co (III) cations to the Co (II) state to increase the rate of leaching of transition metal oxides from the cathode material. At the same time, liquid extraction methods using various organic solvents, in particular, tertiary amines or organophosphorus acids, are used to isolate cobalt and bound metals from the final solution.

[Para 1 5] One document provided, under additional category, a method that includes grinding batteries followed by leaching valuable metals from the resulting powder with a solution of mineral acid in the presence of hydrogen peroxide.

[Para 16] CN106229577A Qinchuan Group Co Ltd 14.1 2.2016) discloses mixed leaching method for positive and negative electrode materials of waste nickel-metal hydride battery, and CN107326181 B Qinchuan Group Co Ltd 1 .9.201 7), that discloses a method for preparing ternary hydroxide from nickel cobalt manganese recycled from used Li-ion batteries through liquid phase method. Both patents disclose use of concentrated acid and hydrogen peroxide for leaching of various metals from scrap battery powder. H2O2 acts as reducing agent and enhance the solubility of metals rather than acting as precipitating agent. [Para 1 7] CN108199103A (to Tianjin Sairuike New Material Technology Co. Ltd. 22.6.201 8), discloses a recycling method of used lead-acid battery by using reactant mixture comprising of citric acid, trisodium citrate and hydrogen peroxide prepared and used for recovery of metals from used batteries. The battery is immersed into the reaction mixture and precipitate is obtained. The precipitate is then burned at elevated temperature to obtain desired metal powder.

[Para 18] KR101 841 700B1 (to Korea Institute of Geoscience and Mineral Resources, 26.3.201 8) disclosed a method for recovering valuable metals selectively from mixed used batteries where the metals are leached from scrap powder obtained from battery using dilute sulphuric acid and then selectively precipitated by changing the pH-value using peroxide-based compounds (which act as oxidising agents) for recovery process.

[Para 19] Another example is EP2444507B1 (to Luidold, Stefan et al.

20.10.2010) which disclosed a method of recycling rare earth metals within a waste material (including batteries), wherein the method comprises acidic leaching of the waste material (particularly in a still pyrolysis solid matter, more particularly in the form of batteries reduced to small pieces are directly made subject of an acidic leaching) using a halogen acid (particularly hydrochloric acid) for solubilizing (or dissolving) metals of the waste material while maintaining nonmetallic materials (such as graphite, plastic or other organic materials) of the waste material in solid form, separating the remaining solid components of the leached waste material from a solution of the solubilized (or dissolved) metals, and precipitating selectively the rare earth metals in the solution while maintaining other metals in dissolved form. The precipitating may comprise adding sulphates (for instance in the form of salts or sulphuric acid) to the solution of the solubilized metals and adding an alkaline solution to the solution of the solubilized metals for increasing the pH-value.

[Para 20] The main disadvantage of the above-mentioned prior art is the fire and explosion hazard of the process of grinding used Li-ion batteries. To avoid such a result, it is necessary to use special equipment for crushing battery scrap in an inert atmosphere, vacuum or liquid environment, which significantly increases the operating and production costs.

[Para 21 ] The disclosed invention provides a method for recovering cobalt and lithium together with other valuable metals in a new safer and simple method.

SUMMARY OF THE INVENTION

[Para 22] Some embodiments of the invention herein relate to the field of Li- ion batteries and, more particularly but not exclusively, to methods for processing Li-ion cells having steel or plastic housings. Specifically, some embodiments relate to methods of separating an electrode of a Li-ion cell from a steel housing that, in some embodiments, have one or more advantages compared to methods known in the art. [Para 23] This hydrometallurgical method for removing metals from used Li- ion batteries teaches a method of dismantling and disassembling all types of Li-ion batteries, mechanical physical destruction of the batteries and separation of mixed electrode cells with cathode material removed to be dissolved by mineral acid containing reduced agent ions, with the extraction of valuable metals from leaching products by traditional methods.

[Para 24] This process also allows a mixture of all types of Li-ion batteries to be processed, including polymer Li-ion batteries, with no costly battery scrap shredding in a liquid or inert environment.

[Para 25] This method shows good technological characteristics in terms of valuable metal recovery, efficiency, and economic feasibility.

[Para 26] The invention may be better understood with reference to the figures.

BRIEF DESCRIPTION OF THE FIGURES

[Para 27] Fig. 1 - A general flowchart of the starting steps of all a embodiments.

[Para 28] Fig. 2 - A flowchart of an embodiment of the method where the Li- ion batteries with plastic housing are manually separated.

[Para 29] Fig. 2a - A continue flowchart of fig.2 showing the 3 options of final solutions of experiment 1 . [Para 30] Fig. 3 - A flowchart of an embodiment of the method of burning/pyrolysis of the Li-ion batteries demonstrated in experiment 4.

[Para 31 ] Fig. 4 - A flowchart of another embodiment of the method of burning/pyrolysis of the Li-ion batteries obtaining cathode material from which metals were extracted. Demonstrated in experiment 5.

[Para 32] Fig. 4a - A continue flowchart of fig 4 testing the extraction of metals.

[Para 33] Fig. 4b - A table showing the different results of experiment 5 when leaching the cathode material in FeSC .

[Para 34] Fig. 5 - A flowchart showing the options of final solution of experiment 10.

[Para 35] Fig. 6 - A flowchart showing a treatment of the Li-ion of experiment 1 1 .

[Para 36] Fig. 6a - A continue flowchart of fig. 6 showing the detailed steps of experiment 1 1 .

[Para 37] Fig. 7 - is a picture of a typical cylindrical electrochemical cell in a steel housing with a protective insulating plastic film.

[Para 38] Fig. 8 - is a picture of a cylindrical cell in a steel case without a protective insulating plastic film.

[Para 39] Fig. 9 - is a picture of a Li-ion cell in a steel case without a protective insulating plastic film, after burning and manual separation of the burned batteries.

[Para 40] Fig. 10 - is a picture showing the Li-ion cell in dissolved iron housing. [Para 41 ] Fig . 1 1 - is picture showing exposed mixed electrode material of crushed Li-ion cell.

[Para 42] Fig. 1 2 - is picture showing isolated cathode material after physicmechanical separation of crushed electrodes material.

[Para 43] Fig. 1 3 - is a graph showing the results of X-ray phase analysis of the isolated cathode material.

[Para 44] Fig. 14 - is a picture showing crushed burned Li-ion cells after magnet separation of crushed material.

[Para 45] Fig. 1 5 - A table- showing the effect of the concentration of H2SO4 on the time required to complete dissolving of iron housing of li-ion cells in experiment 1 .

[Para 46] Fig. 16 - A Table showing the effect of the pH-value of FeSC solution on the recovery of metals in test A of experiment 1 .

[Para 47] Fig. 1 7 - A Table showing the effect of hydrochloric acid (HCI) on the duration of dissolving iron housing of li-ion cells in experiment 2.

[Para 48] Fig. 1 8 - A Table showing the effect of pH-value of FeCL filtered solution on the recovery of metals in experiment 3.

[Para 49] Fig.1 9 - A table showing the results of experiment 4 when using burned Li-ion batteries.

[Para 50] Fig 20 - A table showing the results of burning out of regular Li-ion batteries 103 in experiment 7.

[Para 51 ] Fig. 21 - A table showing the results of burning out of polymer Li- ion batteries in experiment 8. DETAILED DESCRIPTION OF THE DRAWINGS

[Para 52] Fig. 1 is a general flowchart of the beginning of the embodiments. All presented embodiments start from dismantling the electronic equipment and separating the Li-ion batteries in order to get naked Li-ion batteries.

[Para 53] Fig.2 is a flowchart of an embodiment of the method where the Li- ion batteries with plastic housing are manually separated, crushed and tested with FeSo4 with different pH-value.

[Para 54] Fig. 2a is a continue flowchart of fig.2 showing 3 tests of cathode material mixed with FeSo4 with different pH-value from which valuable metals were extracted in experiment 1 .

[Para 55] Fig.3 shows a flowchart of yet another embodiment of the method where the burned Li-ion cells in naked iron housing are magnetically separated as explained in experiment 4 and the results of the 3 tests performed on the leached FeSC solution are shown in the table in fig. 1 9.

[Para 56] Fig. 4 shows the flowchart of experiment 5 describing step by step the recovery of metals from burned il-ions manually separated and processed after dissolving of iron housing.

[Para 57] The flowchart in Fig. 4a describes step by step the 2 test according to experiment 5, where the rate of the extracted metals differs in each test.

[Para 58] The table in fig. 4b shows the comparative results of the 2 tests of experiment 5. [Para 59] Fig. 5 shows a flowchart of experiment 10 where the final solutions of burned Li-ion are differently treated.

[Para 60] Fig. 6 shows a flowchart of the starting steps of experiment 1 1 .

[Para 61 ] Fig. 6a shows a continue flowchart of fig. 6 with detailed steps of experiment 1 1 for recovering NiO, C0304, Fe20s and MnCh.

[Para 62] The table in Fig. 1 5 relates to experiment 1 showing the effect of the concentration of H2SO4 on the time required to complete dissolving of iron housing of li-ion cells. The conclusion from the table teaches that the optimal conditions for completing the dissolving of iron housing is: H2SO4 concentration of 1 .8-2.6 mol/dm3 and stirring for 16-1 8 hours.

[Para 63] The table in Fig. 16 relates to test 1 of experiment 1 showing the effect of the initial pH of the FeSC leach solution on the recovery of lithium and associated transition metals. The conclusion from the table teaches that the optimal pH range for leaching the cathode material is 0.4-0.6, since in a more acidic environment, the solubility of aluminum and copper increases sharply.

[Para 64] The table in Fig. 1 7 relates to experiment 2 showing the effect of the concentration of hydrochloric acid (HCI) on the duration of dissolving iron housing of li-ion electrochemical cells. The conclusion from the table teaches that the optimal conditions for dissolving iron housing is by immersing the li-ion cells in 1 .4-1 .8M of hydrochloric acid (HCI) solution for 12- 18h. [Para 65] The table in Fig. 1 8 relates to experiment 3 showing the effect of the pH range on FeCL filtered solution on the recovery of lithium and associated transition metals. The conclusion from the table teaches that, the optimal pH range for leaching the cathode material is 0.5-0.8, since in the more acidic region, the solubility of aluminum and copper increases sharply.

[Para 66] The table in Fig. 1 9 relates to experiment 4 showing from the tests that the leaching of burned cathode materials 21 3 in sulfuric acid (H2SO4) solution with pH-value of 0.50 recovered a relatively low rate of metals (table in fig.l 9 line 2).

[Para 67] The table in fig. 20 relies to experiment 7 showing that the optimal results for burning out of regular Li-ion batteries 103 is in temperature range of 35O°c - 500°c.

[Para 68] The table in fig. 21 relies to experiment 8 showing that the optimal results for burning out of Li-ion polymer batteries 400 is in temperature above 400°c.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[Para 69] An embodiment is an example or implementation of the inventions. The various appearances of "one embodiment," "an embodiment" or "some embodiments" do not necessarily all refer to the same embodiments.

Although various features of the invention may be described in the context of a single embodiment, the features may also be provided separately or in any suitable combination. Conversely, although the invention may be described herein in the context of separate embodiments for clarity, the invention may also be implemented in a single embodiment.

[Para 70] Reference in the specification to "one embodiment", "an embodiment", "some embodiments" or "other embodiments" means that a particular feature, structure, or characteristic described in connection with the embodiments is included in at least one embodiment, but not necessarily all embodiments, of the inventions. It is understood that the phraseology and terminology employed herein is not to be construed as limiting and are for descriptive purpose only.

[Para 71 ] The present invention relates to an improved process and method for recovering cobalt and lithium together with other valuable metals. The method includes physical separation processes, dismantling and disassembling panels with automotive Li-ion batteries and other battery scrap with the release of plastic, electronic waste and finger Li-ion batteries into separate products, as well as chemical operations, in particular, dissolving the iron body of finger batteries with a sulfuric acid (H2SO4) solution in the presence of hydrogen peroxide.

[Para 72] Before explaining the embodiments in detail, it should be understood that the invention is not necessarily limited in its application to the details of construction and the arrangement of components, or the methods set forth herein. The invention may be practiced in other ways or implemented in various ways. The phraseology and terminology used herein are for descriptive purposes and should not be construed as limiting.

[Para 73] The method hereunder described is performed on solid waste containing Li-ion cells with iron housing. The Li-ion cells having electrodes contained within an iron-containing housing.

[Para 74] As is known in the art, Li-ion cells are typically a component of a Li- ion battery. The battery has a plastic or metal outer housing that houses a plurality of cylindrical Li-ion cells and electronics for monitoring. Each Li- ion finger cell has a cylindrical body containing iron, which is completely or almost completely covered with an insulating coating such as paint or plastic film.

[Para 75] In general, Li-ion cells do not have an open iron-containing housing, but rather the iron-containing housing is covered with an insulated coating and are held inside the battery housing.

[Para 76] As used herein, the term "iron-containing body" refers to a cell casing made of iron or a ferromagnetic iron-alloy containing at least 80% by weight of iron, preferably at least 95% by weight of iron.

[Para 77] As used herein, the term "exposed electrode cells" refers to electrode cells that, after dissolving of the steel body, carry at least 1 5% by weight of residual iron, preferably 2-5% by weight of iron. The electrode cells, when immersed in a reduced solution, at least 40% (preferably at least 60%, at least 80%, at least 90% and even 100%) of the housing outer surface is exposed to contact with the reduced solution. The balance of the housing outer surface that is not exposed to contact with the reduced solution may be coated or covered, e.g., by paint or plastic film.

[Para 78] Provided solid waste containing Li-ion cells having electrodes within an iron-containing housing without an insulating coating includes any number of such Li-ion cells, for example, at least 5% by weight of such Li- ion cells. However, as discussed in more detail below, a particular utility of the teaching herein is such that the teachings are preferably applied to solid waste that includes a relatively higher proportion of Li-ion cells having electrodes inside an exposed iron-containing housing, in some embodiments at least 10%, at least 30%, at least 60% and even at least 75%. In some embodiments, at least 95% by weight of the provided solid waste comprises Li-ion cells having an electrode within an iron-containing housing.

[Para 79] The first step in some embodiments is mechanical separation of Li- ion cells 100 from battery waste, mainly plastic and electronics by dismantling and disassembling 101 EV and all types of Li-Ion batteries and isolate the Li-Ion batteries 102.

[Para 80] In some embodiments, the separation of the Li-ion cells from the battery waste comprises mechanical procedures. Mechanical processing of battery waste includes any suitable method or combination of methods known in the field that separate the Li-ion cells from the other battery components such as battery housing and control electronics, without breaking the Li-ion cell housing. [Para 81 ] Such methods include selective crushing of the plastic case of a battery, separation of plastic, electronics, and Li-ion finger cells and then removing the insulating coating, for example, by placing the batteries in a metal tube equipped with a horizontal hydraulic press, where the plastic case is destroyed by the impact of the press. After that, the material is unloaded and then, by manual separation 301 , electronics and finger-type Li-ion cells 303 are isolated from the plastic 302. The finger-type Li-ion cells are transported along a conveyor to an adjacent apparatus, where the insulating coating is removed from the finger-type Li-ion cells 305 with the help of rotating metal brushes.

[Para 82] According to an aspect of some embodiments set forth herein, there is provided a method for processing Li-ion polymer batteries 400 having an insulating cover film. The insulating cover film is removed 401 , getting naked Li-ion polymer batteries 402.

[Para 83] According to another aspect of some embodiments set forth herein, there is provided a method for processing Li-ion having iron-containing housing covered by plastic film.

[Para 84] The Li-ion batterie's plastic housings are destructed 300 following a manual separation of the destructed batteries 301 into crushed plastic 302 and electronic scrap 303 getting cylindrical EC cells in iron housing, the insulation film of the iron housing is removed 305, getting naked Li-ion cylindrical EC cells in naked iron housing 306 (fig. 1 ). [Para 85] According to yet another aspect of some embodiments set forth herein, there is provided a method for separating cylindrical Li-ion cells from battery waste by burning/pyrolysis of battery scrap 200.

[Para 86] Burned batteries 204 (fig. 1 ) contain cinder. Powdered cinder is the residue of burned components. In embodiments in which the burned batteries include polymer batteries 400, (which do not have an iron housing or electrodes within the iron housing), the residue also contains carbonized polymer battery cells.

[Para 87] In some embodiments, the burnt-out batteries are li-ion cells having electrodes contained in an exposed iron-containing housing that is further processed in accordance with the teachings herein.

[Para 88] In some embodiments, li-ion cells from burned-out batteries are either manually separated from powdered residue, or by gravity separation 210, or by magnetic separation 207, using an electrostatic separator. The separated li-ion cells are further processed as hereunder described. The carbonaceous waste may be used in the cinder blocks production.

[Para 89] In some embodiments, when the burned-out residue contains electrodes, the carbonaceous materials are further processed to recover metals from them, for example, by manual separation or by a vibrating screen.

[Para 90] In some embodiments, residue of electronic components found in common battery cinder are separately processed. In other embodiments, residue of electronic components and polymer batteries 400 are recycled together with li-ion cells as hereunder described.

[Para 91 ] The advantage of some embodiments of separating li-ion cells from plastic components of common batteries by burning is that at least 20-40% of plastic components is significantly reduced, and 100% of the iron body of the finger cells is exposed. The toxicity is reduced, and the risk of inflammation or explosion no longer exists, since in combustion, the fluorinated alcohol in electrolyte burns out, and the fluorinated burned out products are removed through the corresponding safety valve.

[Para 92] Another advantage of separating Li-ion cells from plastic battery components by burning is that when burning predominantly polymer batteries 400 containing a small amount of plastic, significant fuel consumption is required to achieve an optimal combustion temperature (see fig 20 & 21 ). Adding batteries 304 to polymer batteries 400 with a high plastic content, allows reducing gas consumption by 20-30% or diesel fuel by 1 5-20%.

[Para 93] Another advantage of separating Li-ion cells from plastic battery components, by burning the batteries, is that the cinder can be crushed by a standard hammer mill without the risk of inflammation or explosion. The crushed material 206 is subjected to magnetic separation 207, for extracting iron 208, then electronic circuit elements 209 are separated by manual separation, after which the cathode material 21 3 is isolated by gravity separation and screening methods 210. [Para 94] The separated cathode material is leached 21 7 with an iron sulfate solution (FeSC ) 216 obtained by dissolving the previously separated iron 208 with a dilute solution of sulfuric acid (FeSC ) 214 & 21 5. Moreover, burning catalyzes dissolution of iron.

[Para 951 Experiment 1 (fig. 1 & 2)

1 . 20 kg of EV and all types of Li-ion batteries 100 (plastic cartridges for laptop computers containing from 6 to 8 cylindrical Li-ion cells).

2. The Li-ion batteries were opened by a metal pipe comprising a horizontal hydraulic press, the impact force of which is regulated by a programmable regulator, and the impact energy varied from 1 .0 to 8.6 kg. In the course of work, it was found that the optimal work of the press is achieved with an impact energy of 2.0-6.0 kg.

3. Manual dismantling and disassembling 301 . Receiving: ! 8% (by weight) crushed plastic 302, 4% electronic scrap 303, and 78% cylindrical electrochemical cells in an iron housing 304 were obtained.

4. The cylindrical electrochemical cells (1 5.6 kg) with protective insulation 304 (fig. 6) were placed in a powder mill, where the plastic protective insulation was removed in 1 5 minutes 305. 1 5.48 kg of cylindrical EC cells in naked iron housing were obtained 306(fig. i).

5. The cylindrical EC cells in naked iron housing 306 were loaded into 100 liter of plastic reactor containing 78 liters of 2.4M sulfuric acid solution (H ₂ SO ₄ ) 307. 6. The solution was continuously mechanically stirred (300 rpm) 308 during the course of 18 hours. After 1 8 hours, the solution was drained 309. (See table in fig. 1 3)

7. The exposed electrode cells were neutralized with wash water 310.

8. The wash water was mixed with a ferrous sulfate solution (FeSC ) 31 1 .

9. The washed naked il-io cells weighing 1 3.4 kg 312 were crushed by a hammer mill to metal particles 31 3, (copper and aluminum foil) of 2-3 mm. The rest was powdered graphite, carbon and cathode material (mixture of oxides of cobalt, nickel, manganese and lithium) e.g. crushed material 314.

10. The crushed material 314 was separated in sieving and gravity table 31 5 releasing metals foil particles (Cu, Al) 316 and heavy fraction of the cathode material weighing 3.432 kg 31 7.

1 l . The cathode material was divided into 3 equal portions of 1 .144 kg for comparative experiments (318, 319, 320).

[Para 96] Test A: (fig.2a)

1 . 1 /3 quantity of cathode material 318 was mixed with 6 liters of ferrous sulfate solution (FeSC ) at pH-value 0.54 321 .

2. The mixture was stirred continuously.

3. The mixed cathode material was leached at room temperature for 3 hours 322.

4. Thereafter, the productive solution 324 and the insoluble residue 325 were separated by vacuum filtration 323. 5. The precipitate was washed, and the solution was depleted 326.

6. The insoluble residue 325 in the form of a carbonaceous substance, underwent further decomposition in a solution of aqua regia 327.

7. The content of valuable metals in both solutions was determined by ICP spectroscopy method. The degree of extraction of valuable metals into the productive solution was determined by the formula: [Cme ( _P > I (Cme <r) + Cme ( _P ))] x 1 00% = Eme,%, where Cme ( _P > is the metal content in the productive solution, Cme < _r ) is the metal content in the solid residue.

8. As a result of leaching the cathode material with an iron sulfate solution (FeSO ₄ ) at room temperature 321 , the extraction of valuable metals into a productive solution of cobalt, nickel, manganese, and lithium was 98.6%, 94.4%, 92.2%, and 92.6%, respectively 328.

9. To study the effect of the initial pH-value on the leaching solution for recovery of lithium and associated transition metals, 5 portions of 1 00g of insulated cathode material were leached with an iron (II) sulfate solution (FeSO ₄ ) containing 0.56 mol/dm ³ Fe ² with pH-value range 0.20-0.80 for 3 hours in room temperature. The test results are presented in the table in fig.1 4.

[Para 97] Test B:

1 . 1 /3 quantity of cathode material 31 9 was mixed with 6 liters of ferrous sulfate solution (FeSO ₄ ) with pH-value 0.48 329.

2. The mixture 329 was stirred continuously. 3. The mixed cathode material 329 was leached at room temperature for 3 hours 322.

4. Thereafter, leached mixture 322 was separated by vacuum filtration 323 into productive solution 324 and insoluble residue 325.

5. The insoluble residue 325 was decomposed with aqua regia 327.

6. Both solutions were analyzed by the ICP spectroscopy method.

7. The recovery of nickel, manganese, and lithium was 32.3%, 44.2%, 36.7%, and 28.4%, respectively 330.

[Para 98] Test C:

1 . 1 /3 quantity of cathode material 320 was mixed with 6 liters of ferrous sulfate solution (FeSC ) with pH-value 0.48 331 .

2. A 0.43M concentration of hydrogen peroxide solution (H2O2) 332 was fed into the mixture.

3. Mixture 332 was stirred at room temperature continuously for 3 hours.

8. Mixture 332 was separated by vacuum filtration 323 into productive solution 324 and insoluble residue 325.

4. The insoluble residue was decomposed with aqua regia 327.

5. Both solutions were analyzed by the ICP spectroscopy method.

6. The recovery of nickel, manganese, and lithium was 63.7%, 68.3%, 56.8%, and 72.2%, respectively 333.

[Para 99] The results of the tests show that, in equal conditions, ferrous sulfate solution (FeSO ₄ ) with pH-value 0.54 is a more effective leaching agent than sulfate solution (FeSO ₄ ) with pH-value 0.48, even in the presence of hydrogen peroxide H2O2 as a reducing agent (see fig. 14).

[Para 100] Experiment 2

1 . Teatingl 5.0 kg of Li-ion cells with protective insulation 304 with rotating metal brushes. The plastic protective insulation was removed in 5 minutes.

2. 1 5.0 kg of cleaned Li-ion cells were loaded into a 100— liter plastic reactor containing 80 liters of 1 .6 M hydrochloric acid (HCI) solution.

3. The solution was continuously mechanically stirred (300 rpm) for 16 hours, obtaining dissolved Li-ion electrochemical cells. (See table in fig. 1 5).

[Para 101 ] Experiment 3

1 . Leaching 100g of isolated cathode material with ferric chloride (FeCL) solution with initial pH-value range of 0.20-0.80 and O.52mol/dm ³ Fe ² + in room temperature for 3 hours.

2. The objective of the experiment was to learn the optimal pH range for leaching cathode material with ferric chloride (FeCL) solution for recovering lithium and associated transition metals. The experiment results are presented in fig.16.

[Para 102] Experiment 4

1 . Taking 1 Okg of burnt naked Li-ion cells with electrodes 204.

2. Crushing the Li-ion cells 204, with a hammer mill 205 into different sizes of iron particles of about 2-3 mm 206. 3. The crushed material 206 was magnetically separated 207 (18% by weight).

4. The non-magnetic fractions 209 were separated in a sieving and gravity table 210. 2.5kg cathode material 21 3 contaminated with graphite and cinders was release.

5. The cathode material 21 3 was divided into three equal portions of 833g each.

[Para 103] Test A:

1 . The first portion of cathode material 21 3 was mixed with FeSO ₄ solution with pH-value 0.50.

2. The sulfate solution (FeSO ₄ ) 216 was obtained by dissolving the magnetic fraction 208 in 2.04M sulfuric acid (H2SO ₄ ) solution 214.

3. The solution was continuously mechanically stirred (300 rpm) during the course of 1 8 hours. After 18 hours, the solution was drained 21 5.

4. The cathode material 21 3 was mixed with FeSO ₄ solution 216.

5. Mixture 21 7 was leached 218.

6. The leached products were analyzed by ICP spectroscopy method.

7. The following metals were recovered: 98.2% cobalt, 96.4% nickel, 94.3% manganese and 97.2% lithium, as described in the table of fig. 1 7 line 1 .

[Para 104] Test B

1 . The second portion of cathode material 21 3 was mixed with FeSO ₄ solution with pH-value 0.50. 2. The sulfate solution (FeSO ₄ ) 216 was obtained by dissolving the magnetic fraction 208 in 2.04M sulfuric acid (H2SO4) solution 214.

3. The solution was continuously mechanically stirred (300 rpm) during the course of 1 8 hours. After 18 hours, the solution was drained 21 5.

4. The cathode material 21 3 was mixed with FeSO ₄ solution 216.

5. The mixture 21 7 was leached.

6. The leached products were analyzed by ICP spectroscopy method.

7. The following metals were recovered: 58.3% cobalt, 29.6% nickel, 38.8% manganese and 44.3% lithium, as described in the table of fig. 1 7 line 2.

[Para 105] Test C

1 . The experiment on the third portion of cathode material 21 3 repeated Test B but the sulfate solution (FeSO ₄ ) 216 was obtained by dissolving the magnetic fraction 208 in 2.04M sulfuric acid (H2SO ₄ ) solution 214 in the presence of hydrogen peroxide (H2O2).

2. In this case, the following metals were recovered: 62.3% cobalt, 57.5% nickel, 42.3% manganese and 42.6% lithium, as described in the table of fig. 1 7 line 3.

[Para 106] The tests showed that the leaching of burned cathode materials 21 3 in sulfuric acid (H2SO ₄ ) solution with pH-value of 0.50 recovered a relatively low rate of metals (table in fig.l 7 line 2).

[Para 107] Furthermore, the increased rate of the metals recovery, when adding hydrogen peroxide (H2O2), is insignificant (table in fig.l 7 line 3). [Para 108] At the same time, leaching of burned cathode material 21 7 in iron sulfate (FeSC ) solution increases the recovery rate of metals, in comparison with the results of Experiment 1 (table in fig.l 4 line 3).

[Para 109] The conclusion is that, burned iron (II) ions leached in a sulfate medium reduces more effectively cobalt ions (III) to a bivalent state of cobalt (II). It may be assumed that the above factors disrupt the structure of the mixed oxide compound of the cathode material 217, thus increasing the dissolution of the metal oxides.

[Para 1 10] Experiment 5 (fig. 1); (fig. 4)

1 . Taking 1 Okg of burnt Li-ion cells with electrodes 201 (fig. 1 ).

2. The Li-ion cells 201 were manually separated 202, receiving cylindrical EC cells in naked iron housing 204 and iron scrap 203 (fig. 1 ).

3. The EC cells in naked iron housing 204 were placed in a plastic reactor 500.

4. 50 liters of 20% sulfuric acid H2SO4 501 were added to the plastic reactor 500.

5. The mixture 502 was mechanically stirred 503 for 1 1 hours.

6. 80% of the steel housing of 100% of the Li-ion cells 204 was dissolved 504.

7. FeSC solution was obtained with pH-value 0.44 505.

8. The dissolved Li-ion cells 504 were separated from the solution 506.

9. Separated Li-ion cells 504 were rinsed with water and dried 507. 10. Crushing the Li-ion cells 506 with a hammer mill 508.

1 1 . The crushed electrode material 509 contained large strips of metal foil (copper and aluminum), particles of plastics (2-3 mm), fine graphite (0.1 -0.2 mm) and heavy particles of cathode material (0.2-0.3 mm).

12. Using sieving/gravity table 510 for separating crushed material 509. Receiving copper and aluminum particles 51 1 and cathode material, containing less than 10-1 5% carbon 512.

1 3. The cathode material 512 weighing 2.68 kg was divided into two portions of 1 .34 kg each.

[Para 1 1 1 ] Test A - (fig. 4a) l . The first portion 51 3 of cathode material 512 was leached in ferrous sulfate (FeSO ₄ ) with pH-value 0.44 containing mol/dm3 of: 0.014 Al, 0.0031 Co, 0.0020 Cu, 0.50 Fe, 0.01 1 Li, 0.0032 Mn, 0.001 2 Ni at room temperature for 3 hours 514.

2. Receiving FeSO ₄ with pH-value 1 .8 containing, mol/dm3 of: 0.03 Al, 0.73 Co, 0.031 Cu, 0.53 Fe, 0.92 Li, 0.026 Mn, 0.063 Ni 51 5.

3. The extracted metals were Co 98.82%, Ni 95.83%, Mn 95.61% and Li 97.62% as shown in the table at line 1 of fig. 4b) 516.

[Para 1 12] Test B (fig. 4b)

1 . The second portion 51 7 of cathode material 512 included ferrous sulfate (FeSO ₄ ) with pH-value 0.52 containing mol/dm3 of: 0.03 Al, 1 .29 Co, 0.031 Cu, 0.53 Fe, 0.92 Li, 0.026 Mn, 0.063 Ni + H ₂ SO ₄ 518

2. The mixture was leached in room temperature for 3 hours 519. 3. The extracted metals were Co 94.56%, Ni 90.67%, Mn 92.34%, and Li 87.42% as shown in the table at line 2 of fig. 4b) 520.

[Para 1 1 3] It should be noted that the slight increased recovery of metals in this experiment in comparison with the table in fig.16, results from the direct dissolution of the steel housing of the Li-ion cells. There are losses of cathode material when separated magnetically from crushed material, as described in experiment 1 .

[Para 1 14] Experiment 6.

1 . 1 .5 kg of crushed electrode material 509 containing, in addition to graphite, carbon and cathode material, 6.3% copper and 2.6% aluminum.

2. Material 509 was mixed with a mixture of 20% citric acid solution (CeHsO?) and ferrous sulfate solution (FeSC ) with a pH-value of 0.64 in ratio of 4: 1 .

3. Stirring (300 rpm) leaching the mixture in room temperature for 3 hours to solid ratio of 5: 1 .

4. The extraction of lithium and transition metals was, wt: 96.52% Li, 94.56% Co, 97.35% Ni and 93.72% Mn.

5. At the same time, the extraction level of aluminum and copper particles from the solution did not exceed 2.6% and 5.3%, respectively.

6. Particles of copper and aluminum foil remained practically unaffected in the leaching process and can be additionally recovered by screening. [Para 1 1 5] The conclusion of the experiment teaches that the use of citric acid (CeHsO?) in combination with a solution of ferrous sulfate (FeSO4) as a leaching agent makes it possible to reduce the number of technological operations without reducing the efficiency of the main technological indicators.

[Para 1 16] Experiment 7. (fig.20)

1 . 10 kg of regular Li-ion batteries 103 were divided into four parts and burned in temperature range of 250°c-650°c.

2. The analysis of the burnt Li-ion polymer batteries showed that the optimal complete burning conditions occurs at temperatures between 3500c - 5000c.

[Para 1 1 7] Experiment 8. (fig.21 )

1 . 10 kg of polymer Li-ion batteries 400 were divided into four parts and burned in temperature range of 250°c-650°c.

2. The analysis of the burnt Li-ion polymer batteries showed that the optimal complete burning condition occurs at temperatures above 400°c.

[Para 1 18] Experiment 9.

1 . 10 kg of polymer Li-ion batteries were mixed with 3 kg of Li-ion batteries in plastic housing and burned in temperature of 400°c.

2. Due to the combustion of the plastic, the temperature in the burning equipment rose to 500°C, and the mixed butteries were completely burned out. 3. The conclusion of the experiment shows that the burning of mixed battery waste containing more than 20% of Li-ion batteries in plastic housing can reduce the initial operating temperature from 55O°c to 400°c, which accordingly reduces fuel consumption and economize the process.

[Para 1 19] Experiment 10. (fig. 5)

1 . 1 1 L of a final solution 1 220 composed of, mol/dm3: 0.03 Al, 0.73 Co, 0.031 Cu, 0.53 Fe, 0.92 Li, 0.026 Mn, 0.063 Ni was prepared for isolating lithium, cobalt, nickel and manganese.

2. The solution was neutralized with NaHCOs solution to pH-value 4 221 .

3. The neutralized solution 221 was continuously stirred and oxalic acid powder H2C2O4 was added in ratio of 1 .5 mol of acid for each mol of iron, cobalt, nickel and manganese salts contained in the solution 222.

4. The pH-value of the solution was adjusted to 9.8 with an alkaline solution 223.

5. The cumulative oxalate precipitate was completed within 3 hours 225.

6. The precipitate was filtered, washed, dried 225.

7. The filtered precipitate 225 was burned at 55O°c for 3 hours 226.

8. The resulting sediment weighing 0.1 1 1 kg contained, wt: 52.2% Co, 36.9% Fe, 4.8% Ni, 2.01 % Mn, 0.004% Al and 0.16% Cu 228.

9. The phases of resulting sediment 228 were: cobalt was in the form of trioxide CO3O4, iron in the form of FesC , nickel in the form of (Nickel (II) oxide) NiO, and manganese in the form of (Manganese (II) oxide) MnO2.

10. Since magnetite (Fe3O4) is a ferromagnetic compound, cobalt trioxide is paramagnetic, and nickel and manganese oxides are non-ferromagnetic, iron oxide was selectively isolated from mixture 228 by low-frequency electromagnetic field of 160W/g with a frequency of 5.2 kHz. 236.

1 1 . The Degree of extraction of Iron was 86% and loss of cobalt was 8.6% 239.

1 2. The resulting product 237 of the magnetic separation 236 was a mass of 0.069.4 kg it may be additionally purified and used in the production of cathode material 240.

1 3. Lithium 232 was isolated and filtrated from the entire oxalate precipitate 224 by evaporation 231 of the solution 230 to a lithium content of 1 .8 mol/dm3. Thereafter, NaHCOs 232 was added to the solution with vigorous stirring.

14. The formation of poor soluble lithium carbonate ended within 2 hours 233.

1 5. The precipitate was separated from the solution by vacuum filtration, washed, and dried 234. The resulting product 235 can be used together with the collective precipitate of cobalt, nickel and manganese oxides 237 in the production of cathode material for Li-ion cells 240.

[Para 120] Experiment 1 1 (fig. 6 & fig. 6a) 1 . Manganese (II), iron (II) and cobalt (II) were successively extracted from a productive solution 261 with a final pH-value of 1 .8 composing mol/dm ³ : 0.03 Al, 0.73 Co, 0.031 Cu, 0.53 Fe, 0.92 Li, 0.026 Mn, 0.063 by liquid-liquid extraction with 0.5 M solution of Cyanex 272 in kerosene 262.

2. For this, the pH-value of the initial productive solution 253 was brought to 2.86 using a 1 2.5M NaOH solution.

3. Solution 253 was mixed with organic solvent 256 at a phase ratio O:L = 1 : 1 and stirred for 1 5 min.

4. As a result, it was possible to isolate 89% iron and 92% manganese into the organic phase 263 in final solution l a, while cobalt was extracted only by 3.4%.

5. From the organic phase 254, iron and manganese were stripped 255 with a 1 .5 M H2SO4 solution at a phase ratio O: L = 8: 1 .

6. For the complete separation of cobalt from the first raffinate, the pH- value of the aqueous phase 261 was brought to 5.4 262 and, in final solution 1 b 270 in equal conditions, it was possible to transfer 94% of cobalt and only 2.2% of nickel into the organic phase 263.

7. Cobalt was re-extracted with 2.1 M H2SO4 solution at O: L ratio of 8: 1266. . Manganese and iron 257 were precipitated from the sulfuric acid solution 255 in the form of hydroxides 258. 9. Cobalt was isolated from the re-extract from sulfuric acid solution 266 in the form of oxalate 267. 0. Precipitation 267 was washed, dried, and burned at 55O°C, and trioxide was obtained with a content of less than 2.5% of associated metal impurities. 1 . Nickel from the second raffinate 272 was precipitated at pH-value 9.8 in the form of insoluble oxalate.