Method for upgrading materials obtained from end-of-life lithium-ion batteries

Abstract

The present invention relates to a method for selectively upgrading the elements in a material obtained from a mixture of end-of-life batteries. The invention relates more particularly to the field of upgrading the metal elements including cobalt, nickel and manganese present in the materials obtained from end-of-life lithium-ion batteries. The present invention also presents a solution for upgrading lithium and also graphitic carbon, in the form of lithium carbonates and graphitic carbon in the case where the material originates from rechargeable batteries. The method that is the subject of this invention thus makes it possible to upgrade the elements contained in a material obtained from end-of-life lithium-ion batteries so as to have new products that can be used for a second use for the preparation of active materials for lithium-ion batteries.

Description

[0001] Process for recovering materials from end-of-life lithium-ion batteries

[0002] OUZAOUIT Khalid, LAMSAYETYI Isam, FAQIR Hakim, BENZAKOUR Intissar

[0003] FIELD OF THE INVENTION

[0004] The present invention relates to a method for selectively recovering the elements included in a material from a mixture of end-of-life batteries.

[0005] The invention relates more particularly to the field of the recovery of metallic elements including cobalt, nickel, manganese present in materials from end-of-life lithium-ion batteries, the present invention also presents a solution for the recovery of lithium as well as graphite carbon, in the form of lithium carbonates and graphite carbon in the case where the material comes from rechargeable batteries, the process which is the subject of this invention therefore makes it possible to recover the elements contained in a material from end-of-life lithium-ion batteries in such a way as to have new products which can be used for a second use for the preparation of active materials for lithium-ion batteries.

[0006] PREVIOUS ART

[0007] The growing demand for elements used in lithium-ion batteries and in particular, in electric mobility applications continues to increase day by day for economic and environmental reasons. Lithium-ion batteries are in high demand for the performance they offer in terms of (I.Akalay et al, WO 2010, 150038):

[0008] ■ Good energy storage capacity

[0009] ■ Good thermal stability

[0010] ■ Long lifespan

[0011] The quantity of end-of-life lithium-ion batteries generated and the scarcity of metals used in their manufacture represent, among other things, economic and environmental concerns of great importance and criticality. The recovery of all the elements present in the materials from end-of-life lithium-ion batteries therefore becomes an undeniable necessity. The main elements concerned include cobalt, nickel, manganese, lithium and graphite carbon, the demand for which continues to increase day by day and in an exceptional manner in order to meet the needs of electric mobility and more specifically in the materials applied in lithium-ion batteries.

[0012] The scarcity of cobalt, nickel, and manganese mineral resources and the decrease in reserves, as well as the growing demand for these elements, accompanied by industrial developments and the evolution of electric mobility, has created a challenge related to the recycling and recovery of the elements contained in lithium-ion batteries. The subject of recovering valuable elements contained in lithium-ion batteries remains a fertile field of intense investigation in order to develop appropriate processes for the recovery of these elements. For example, 400,000 tons containing the active materials of lithium-ion batteries will be generated by 2025, which represents an economic challenge of $2.6 billion (Melin et al., 2018).

[0013] In this context, two ways for the recovery of elements included in lithium-ion batteries have been the subject of several inventions, namely hydrometallurgical processes and pyrometallurgical processes. Hydrometallurgical processes are generally preferred for this type of treatment, this is mainly attributed to the high energy consumption of the thermal treatments implemented in pyrometallurgical processes as well as the environmental problem due to the generation of polluting and toxic gases. In addition, pyrometallurgical processes do not allow optimal recovery of the elements, mechanical losses in the form of dust or in the slag in the form of oxides are among the limiting points of this type of process.

[0014] On the other hand, hydrometallurgical processes present a solution of choice that does not involve large energy consumption. Another advantage of hydrometallurgical processes compared to pyrometallurgical processes is the recovery of lithium, which is a valuable element in lithium-ion batteries. Both types of processes face several challenges, namely: the operating cost of the operations, the quality of the products obtained and the metal recovery yields. The recovery selectivity in the case where the elements are to be recovered separately, as well as the difficulty of recovering both the elements constituting the cathode and the anode of lithium-ion batteries. Both processes are also generally confronted with the types of impurities often present in this type of material.

[0015] Separating the materials that make up the cathode and anode of batteries is often difficult, which makes the recovery of all the elements from end-of-life lithium-ion batteries difficult.

[0016] In this context, document WO-2020-092157-A1 describes a hydrometallurgical process for recovering cobalt and lithium by means of an acid attack in the presence of sodium thiosulfate; said process proposes a process consisting of placing the battery cathode materials in acid solution in the presence of a reducing agent, followed by purification steps to remove impurities such as aluminum, iron and manganese and subsequently recovering the elements cobalt, nickel and lithium present in the cathode of lithium-ion batteries; said process has the limitation in terms of recovering only the cathode material commonly known by the term "CAM: Cathode active material" of lithium-ion batteries and more particularly cobalt and lithium.However, it is known that it is generally difficult to separate the cathode and anode elements (consisting mainly of graphite deposited on copper foil in addition to the impurities existing in lithium-ion batteries) for the processing of a large volume of lithium-ion batteries.

[0017] PCT document: US 2021 / 040203 proposes a solution for the recovery of the elements Co, Ni and Mn contained in the black mass, the separation is carried out by oxidation of manganese in the form of MnC and the preparation of a Co / Ni alloy by electrolysis, the dissolution was carried out using an acid by adding SO2 gas as a reducing agent. This process has the limitation in terms of recovery of cobalt and nickel in the form of a Co / Ni alloy and does not subsequently allow the recovery of each element separately, namely cobalt and nickel, which leaves the possibility of their reuse in the battery difficult (circular economy). On the other hand, said process does not address the recovery of manganese which, once eliminated in the form of MnC, requires several additional and expensive treatments to recover the manganese, this invention does not address the recovery of lithium and graphite carbon present in the black mass.

[0018] Patent EP3950977A1 ​​claims a process for recovering cobalt, manganese and nickel in the form of metal lactate from a material containing cobalt, nickel and manganese. The dissolution was carried out by adding lactic acid, this document gives no indication concerning lithium or graphite, generally present in this type of residue which is the subject of the invention. Document PCT / CA2021 / 050663 claims a process for dissolving cobalt, nickel, manganese and precipitating one or more elements at a time using formic acid. This patent has the limitation in the sense that the recovery of lithium requires a thermal decomposition treatment at a temperature between 270C and 450 < C.

[0019] In the paper "Recovery and Recycling of Lithium: A Review" the authors reviewed all the technologies used for lithium recovery from different sources and concluded that there is no technically and economically sound process for lithium recovery from lithium-ion batteries.

[0020] Document US005888463A describes a process for recovering lithium contained in end-of-life battery waste. The claimed process consists of cryogenic cooling of the waste containing lithium followed by grinding and then dissolution with sulfuric acid. The resulting solution undergoes electrolysis and then a reaction with a flow of CO2 in order to form Ü2CO3. The said patent gives no indication of the other elements generally present in materials from end-of-life batteries.

[0021] Patent WO 2020 / 160615 proposes a process for recovering lithium in the form of lithium hydroxide, said process comprises several steps consisting of exploiting the fact of the low solubility of sodium sulfates at low temperatures (<10C) then recovering the lithium in the form of hydroxide, other steps of redissolution, purification and crystallization make it possible to obtain lithium hydroxides; said process has the limitation in terms of the number of steps to be applied in said process which makes its industrial feasibility delicate.

[0022] The present invention provides a solution for the recovery and recycling of cobalt, nickel and manganese metals present in materials from used batteries. The present invention advantageously provides, among other things, the recovery and recycling of lithium and graphite carbon.

[0023] The process also allows preferentially to develop high added value derivatives based on cobalt, nickel, manganese, lithium and graphite carbon which can be used for the preparation of new active materials for lithium-ion batteries.

[0024] Another advantage of the present invention consists of the recovery of all the elements present in the materials from end-of-life lithium-ion batteries by a hydrometallurgical process.

[0025] The materials recovered by the process of the present invention could be reused for the preparation of new active materials for lithium-ion batteries, thus giving them the possibility of use within the framework of a circular economy.

[0026] DESCRIPTION OF THE INVENTION

[0027] The object of the invention is to propose a process for recovering the elements contained in a material based on cobalt, nickel, manganese and lithium. More advantageously, the present invention claims a process for recovering the elements present in materials from end-of-life lithium-ion batteries or any type of material comprising cobalt, nickel, manganese and lithium.

[0028] These materials will subsequently be referred to as “Black-mass”. It is recalled that black-mass generally comes from materials contained in end-of-life batteries and / or in lithium-ion battery production waste; consequently, these materials include cobalt, nickel, manganese, lithium and graphite in addition to copper, aluminum and other impurities and / or their combinations.

[0029] In the remainder of the present invention, materials from end-of-life batteries and / or battery production waste will be referred to by the term “Black-mass”.

[0030] Another advantage of the present invention concerns the recovery of elements also present in the cathode and in the anode of lithium-ion batteries.

[0031] According to the characteristics of the invention, the process that is the subject of this invention provides a solution for separately recovering the elements cobalt, nickel, manganese and lithium in the form of high added value derivatives that can be used for the preparation of new active materials for lithium-ion batteries. In an innovative manner, the process makes it possible to prepare derivatives of nickel (nickel hydroxides and / or sulfates), manganese (in the form of manganese carbonates), lithium (in the form of lithium carbonates), cobalt in the form of metal and also graphite carbon. Another advantage of the process that is the subject of the present invention is that it can be applied to any type of material from end-of-life batteries including cobalt, nickel, manganese and lithium.

[0032] The method which is the subject of this invention has several advantages in terms of:

[0033] ■ Recovery yields of Co, Ni, Mn, Li and graphite carbon elements

[0034] ■ Cobalt is recovered in the form of a very high purity metal (>99.99%) which can be used in several applications, for example in the preparation of salts used in the field of lithium-ion batteries, in catalysis and / or in cutting tools.

[0035] ■ Nickel is recovered in the form of nickel hydroxides and / or nickel sulfates and can be used in the preparation of new active materials in lithium-ion batteries

[0036] ■ Lithium is recovered in the form of lithium carbonates with battery quality, which makes it suitable for use in the preparation of active materials for lithium-ion battery cathodes.

[0037] ■ Graphite is preferentially recovered for possible reuse in the field of lithium-ion batteries.

[0038] ■ According to a well-defined embodiment, all of the elements included in the materials from end-of-life lithium-ion batteries have been recovered in the context of a circular economy allowing the reuse of the products generated from the process of the present invention in the preparation of new materials applicable in the field of lithium-ion batteries, in catalysis or any other field using these materials based on cobalt, nickel, manganese, lithium and / or their combinations. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Other features and advantages of the invention will become apparent upon reading the detailed description. Below is a description of the figures and tables cited in this invention.

[0040] List of figures

[0041] Figure 1: Flow-sheet for the valuation of “black mass”

[0042] Figure 2: X-ray diffraction pattern of a black-mass sample

[0043] Figure 3: SEM characterization of the typical black-mass sample

[0044] Figure 4: X-ray diffraction pattern of residue A: Graphite carbon

[0045] Figure 5: Scheme for the preparation of nickel hydroxides

[0046] Figure 6: X-ray diffraction pattern of nickel hydroxides produced from the raffinate (Ni, Li),

[0047] Figure 7: Protocol for the preparation of nickel sulfates

[0048] Figure 8: X-ray diffraction pattern of nickel sulfates made from end-of-life lithium-ion battery material

[0049] Figure 9: DRX characterization of lithium carbonates

[0050] List of tables

[0051] Table 1: Chemical analysis of a sample of black mass

[0052] Table 2: Leaching performance of a typical black mass sample

[0053] Table 3: Profile of solutions obtained following the dissolution of materials from end-of-life lithium-ion batteries (black mass)

[0054] Table 4: Precipitation performance at pH=6

[0055] Table 5: Profile of the solution used for liquid-liquid extraction

[0056] Table 6: Typical power solution profile

[0057] Table 7: Aqueous phase

[0058] Table 8: Organic phase profile

[0059] Table 9: Chemical profile of solution B (Co, Mn)

[0060] Table 10: Chemical profile of solution C (Ni, Li)

[0061] Table 1 1: Operating conditions for solvent separation of Co / Mn

[0062] Table 12: Monitoring of aqueous phases during the five extraction stages Table 13: Monitoring of organic phases during the five extraction stages

[0063] Table 14: Monitoring of organic phases during the three washing stages

[0064] Table 15: Chemical quality of cobalt cathode

[0065] Table 16: Chemical analysis of prepared nickel hydroxide

[0066] Table 17: Chemical analysis of nickel sulfates produced from end-of-life lithium-ion battery material

[0067] Table 18: Chemical quality of I 2CO3

[0068] Table 19: Structural parameters of the produced lithium carbonates Li2CÛ3

[0069] DETAILED DESCRIPTION OF THE INVENTION

[0070] The method described in the present invention presents an advantageous and economical solution applicable on an industrial scale for the recovery of elements contained in a material from end-of-life lithium-ion batteries and / or any material comprising cobalt, nickel, manganese, lithium and graphite and / or their combinations. The present examples illustrate the invention without, however, limiting it.

[0071] EXAMPLE 1:

[0072] The overall flow sheet produced according to an embodiment of the present invention comprises the following steps:

[0073] Dissolution of matter including cobalt, nickel, manganese, lithium and graphite carbon.

[0074] Figure 1: Flow-sheet for the valuation of “black mass”

[0075] It is recalled that one of the original features of the process of the present invention is that it allows the recovery of the elements contained in end-of-life Li-ion batteries regardless of the composition they contain. It also allows the recovery of lithium-ion battery production waste; these materials are commonly known as black mass.

[0076] Subsequently, the term “Black-mass” will be adopted to designate materials from end-of-life batteries and / or lithium-ion battery production waste.

[0077] It should be remembered that the active materials of the cathode of lithium-ion batteries have a variable composition and in particular, the metals (Co, Ni, Mn, Li, Al, Cu, Carbon graphite) which vary depending on the technology of the battery manufacturer.

[0078] As an illustration, the characterization of the black mass object of our invention shows that the percentage of cobalt varies from 0.2% to 30%, the percentage of nickel varies between 1.2% and 36%, the percentage of manganese varies from 0.2 to 24% According to an embodiment of the present invention, the chemical analysis of the material object of this study is presented in the table Table 1: Chemical analysis of a sample of the black mass a) Structural characterization of the black-mass material obtained from lithium-ion batteries

[0079] The following figure illustrates the X-ray diffraction pattern of the said material:

[0080] X-ray diffraction characterization shows that the product consists mainly of LiMC oxide with M: Ni, Co, Mn.

[0081] X-ray diffraction revealed the presence of secondary phases attributed mainly to graphite carbon, aluminum oxide.

[0082] Figure 2: X-ray diffraction pattern of a black-mass sample

[0083] The characterization by scanning electron microscope (Figure 3) of the black mass object of our invention shows that the grains constituting the sample present heterogeneous morphologies. In the case object of this example, we note the presence of several types of distinct morphologies:

[0084] The first morphology corresponds to spherical secondary particles suitable for battery applications (ÜMO2).

[0085] The second morphology corresponds to agglomerations of cobalt, manganese and nickel oxide particles. These particles, whose morphology is not regular and whose analysis (EDS) shows that they are indeed oxide (NMC). We also note the presence of carbon incorporated within the Ni, Co and Mn oxide grains. We also note the presence of almost spherical graphite carbon grains.

[0086] Figure 3: SEM characterization of the typical black-mass sample b) Controlled dissolution of the black-mass by acid attack in the presence of H2O2 The dissolution is carried out using sulfuric acid with a controlled addition mode, the controlled parameters are the addition mode, the flow rates, the temperature, the potential, and the pH. According to one embodiment, the dissolution was carried out via the simultaneous addition of sulfuric acid and hydrogen peroxide.

[0087] The addition of H2O2 is preferably carried out according to the process which is the subject of this invention in a progressive manner with a controlled flow rate. The addition is carried out in the presence of sulfuric acid. Under the conditions of implementation according to the process of the present invention the reaction is exothermic. It is obvious that H2O2 acts as a reducing agent to convert the insoluble elements of valence +4, +3 present in the oxides ÜMO2 where M: Ni a CobMn c (with a+b+c=1) into elements having valences +2 soluble by means of the reaction below:

[0088] LiNiaCobMncC + ((a+b+c) + 0.5) H2SO4 + 1 / 2H2O2a N1SO4 + b CoSO4 + c M11SO4 + 0.5Li2SO4+ 2 H2O (1) c) Characterization of residue “A” obtained following the leaching step

[0089] The residue "A" obtained following the dissolution of the material from end-of-life lithium-ion batteries was characterized by X-ray diffraction and the analysis of the diagram obtained confirms the production of graphite carbon in accordance with the standard file ASTM 00-041-1487. No additional lines were detected by X-ray diffraction.

[0090] Figure 4: X-ray diffraction pattern of residue A: Graphite carbon

[0091] The purity of the obtained graphite carbon exceeds 94% and has been improved following moderate acid washing to reach a purity exceeding 98%.

[0092] This original result shows the possibility of recovering the graphite carbon contained in the black mass in addition to the recovery of metals which will be the subject of the following examples. d) Performance of acid leaching H2SO4 in the presence of H2O2

[0093] The performances obtained relating to acid leaching are illustrated in the following table Table 2: Leaching performances of a typical sample of black mass

[0094] Table 2 shows that the dissolution of cobalt, nickel and manganese is carried out according to the embodiment of the present invention with a yield of 99%. It is also noted that the dissolution yield of lithium according to an embodiment of this invention exceeds 99%.

[0095] Generally speaking, the solutions obtained following the step of dissolving materials from end-of-life lithium-ion batteries (black mass) can present very variable profiles depending on the composition of the material treated. The following table illustrates the variation ranges that could be presented by the solutions obtained following the leaching of materials from end-of-life lithium-ion batteries (black mass):

[0096] Table 3: Profile of solutions obtained following the dissolution of materials from end-of-life lithium-ion batteries (black mass)

[0097] Example 2: Purification of the solution obtained following the leaching of a sample of the black mass

[0098] According to an embodiment of the present invention, the step of purifying the solution obtained following the protocol of example 1, This step consists of eliminating the impurities by increasing the pH varying between 5.5 and 6.2 by adding sodium carbonate. According to said preferred embodiment of the present invention, the pH of the order of 6 makes it possible to achieve precipitation yields of impurities, in particular iron, aluminum and copper, exceeding 99%.

[0099] The performances obtained for the elimination of impurities (Fe, Al, Cu) are shown in Table 4. Table 4: Precipitation performances at pH=6

[0100] Solution profile (g / l) 25.74 0.73

[0101] Purified solution profile (g / l) 17.11 0.001

[0102] Treatment at pH = 6 allows total elimination of iron, copper and aluminum with a yield greater than 99%.

[0103] Example 3: Separation of Co, Mn / Ni, Li:

[0104] According to an embodiment of the present invention, the method of this invention consists in subjecting the leaching solution of the black mass after its purification at pH 6 to separation by organic solvent. This solution comprises cobalt, manganese, nickel and lithium to liquid-liquid extraction operations by solvent composed of two stages. The first stage aims at the separation of cobalt and manganese from nickel and lithium. The second stage consists in selecting and concentrating the nickel from lithium and subsequently producing a high-purity nickel sulfate solution. The latter will be used to produce nickel hydroxides and nickel sulfates.

[0105] The separation of cobalt from manganese was carried out using the phosphinic acid solvent “lonquest 290”.

[0106] The order of extraction of metals for the solvent lonquest 290 at increasing pH is well established and is as follows: Mn > Co » Ni > Li. a) Conditions for the separation Co, Mn / Li, Ni

[0107] According to an embodiment of the present invention, the applied scheme is composed of three extraction stages at pHs of 4.5 and 5.3, a solvent washing stage with a cobalt sulfate solution, a back-extraction stage at pH 0.2-1.8. At the end a regeneration stage of the back-extracted solvent with sulfuric acid.

[0108] It is noted that in one embodiment of the present invention, the input solution to the various solvent separation steps could have variable profiles depending on the composition of the black masses comprising the material from end-of-life lithium-ion batteries and / or production waste from the lithium-ion batteries being processed. Indeed, said solution may have the profile listed in the following table:

[0109] Table 5: Profile of the solution used for liquid-liquid extraction

[0110] According to an embodiment of the present invention, an example of the typical input solution of the liquid-liquid separation steps by organic solvent is illustrated in Table 6 and will subsequently be the subject of the study. It should however be noted that all the steps of the process remain valid for the input solutions having the profile listed in Table 5.

[0111] Table 6: Typical power solution profile

[0112] A NaOH solution is used to adjust the pH of the solution entering the liquid-liquid separations to the desired value.

[0113] The acidic organic extractant used as the organic phase was prepared by diluting phosphonic acid (lonquest 290) to a concentration of 24% by volume. The extraction temperature is maintained in the range between 25 and 35 <0, The extraction pH is between 4.6 and 5.8, The O / A ratio in the extraction step varies between 2.3 and 2.6,

[0114] The concentrations of the elements cobalt, manganese, nickel and lithium obtained in the aqueous and organic phases after extraction are shown in Tables 7 and 8 respectively. O: Organic phase;

[0115] A: Aqueous phase,

[0116] Table 7: Aqueous phase

[0117] The solvent profile in the extraction circuit obtained according to an embodiment with an O / A ratio varying between 2.3-2.6 is listed in Table 8.

[0118] Table 8: Organic phase profile

[0119] As can be seen from the results presented in Table 1, both cobalt and manganese concentrations in the feed solution were reduced to 0.001 g / l by a three-stage countercurrent extraction. The extraction yields of cobalt and manganese are 99.9% and 99.9%, respectively. This result allows the selective separation of Co and Mn from Ni and Li.

[0120] It should be noted that the acidic organic extractant containing 0.018 g / L of extracted nickel can be subjected to washing in order to recover the nickel from the organic phase. Washing the loaded solvent at a pH equal to 4.4 reduces the concentration of extracted nickel in the loaded solvent from 0.28 g / L to 0.018 g / L.

[0121] This embodiment subsequently allows two solutions to be obtained (B and C)

[0122] The profiles of solutions B and C are listed in tables 9 and 10,

[0123] Table 9: Chemical profile of solution B (Co, Mn)

[0124] Table 10: Chemical profile of solution C (Ni, Li)

[0125] Example 4: Separation of Co / Mn: a) Co / Mn separation by organic solvent: According to an embodiment of the present invention, the solutions obtained following the application of the steps described in Example 3, in particular, solution B which contains 10.1 g / l of manganese and 11.18 g / l of cobalt. The cobalt / manganese separation was carried out according to the steps in Table 11. The solvent used in this case is P204 (24%)

[0126] Table 1 1: Operating conditions for solvent separation of Co / Mn

[0127] The composition of the solution obtained following the solvent extraction step is presented in Table 12.

[0128] Table 12: Monitoring of aqueous phases during the five extraction stages It is noted that the Co / Mn ratio in the feed solution is of the order of 1.1, increasing to a value of the order of 38633 in the manganese-purified solution.

[0129] Table 13: Monitoring of organic phases during the five extraction stages

[0130] Cobalt extracted with manganese is recovered in the washing step, as shown by monitoring the organic phase during the three-stage washing.

[0131] Table 14: Monitoring of organic phases during the three washing stages

[0132] According to one embodiment, the composition of the concentrated cobalt solution is

[0133] 50.24 g / l in cobalt and 0.001 g / l in manganese b) Preparation of the high purity cobalt cathode (99.99%)

[0134] According to one embodiment of the present invention, the typical solution from Example 4 underwent electrolysis to obtain a high-purity cobalt cathode. The electrolysis was carried out according to one embodiment of the present invention under the following conditions: Current density: 220 A / m 2Co concentration: 50 g / l pH: 2.6 Temperature: 60 C

[0135] The following table illustrates the quality of the prepared cobalt cathode

[0136] Table 15: Chemical quality of the cobalt cathode:

[0137] Example 5: Valuation of nickel

[0138] The solution resulting from the liquid-liquid extraction operation referenced by C resulting from the application of the protocol of example 3 was used for the production of two nickel derivatives, namely: nickel hydroxides and nickel sulfates. In the following, the two protocols will be presented. The residual lithium in the exhausted solution was also recovered in the form of lithium carbonates. a) Recovery of nickel in the form of nickel hydroxides.

[0139] The process developed in this first version consists of recovering the elements Ni, Co. In fact, following the solvent extraction operation (lonquest 290), a solution is obtained which contains nickel and lithium.

[0140] Figure 5: Scheme for the preparation of nickel hydroxides. The chemical analysis of nickel hydroxides prepared from the raffinate (Ni, Li) is listed in the following table:

[0141] Table 16: Chemical analysis of prepared nickel hydroxide

[0142] [*]: Ni purity is determined by the formula: 100-^impurities

[0143] The humidity of the produced nickel hydroxides varies between 70% and 75%. b) Characterization by X-ray diffraction

[0144] X-ray diffraction characterization of the product obtained by precipitation of Ni referenced by C, shows that the diagram obtained presents the characteristic lines of nickel hydroxide in accordance with the standard file ASTM 01 - 073-1520,

[0145] It is also noted that the diagram (DRX) of the product obtained presents very broad lines attributed to a crystallite size effect (nanometric),

[0146] Figure 6: X-ray diffraction pattern of nickel hydroxides produced from the raffinate (Ni, Li) c) Recovery of nickel in the form of nickel sulfates

[0147] The recovery of nickel in the form of nickel sulfates was carried out according to the protocol described in the figure (figure 7). In fact, the nickel hydroxides prepared according to the protocol described in example 5 undergo dissolution followed by evaporation and crystallization.

[0148] Figure 7: Protocol for the preparation of nickel sulfates X-ray diffraction characterization of the product obtained confirms that it is indeed nickel sulfates NiSO4, 6 H2O.

[0149] X-ray diffraction characterization of the crystals produced shows the formation of a single phase based on hydrated nickel sulfates. The X-ray diffraction pattern is shown in the following figure.

[0150] Figure 8: X-ray diffraction pattern of nickel sulfates produced from material from end-of-life lithium-ion batteries (black - mass)

[0151] It is noted that the product obtained presents the characteristic lines of nickel sulfates, the diagram (DRX) shows that it is a well crystallized product. No additional lines were detected by X-ray diffraction.

[0152] The profile of the nickel sulfates produced is listed in the following table: Table 17: Chemical analysis of nickel sulfates produced from material from end-of-life lithium-ion batteries

[0153] Example 6: Valorization of lithium in the form of Li2CO3

[0154] The exhausted solution resulting from the precipitation of nickel hydroxides has a lithium concentration of around 5 g / L. The process which is the subject of the present invention advantageously allows the recovery of lithium by precipitation of lithium in the form of lithium carbonates. The precipitation yield of lithium in the form of lithium carbonates reaches 65%.

[0155] - The precipitation yield of Li2CO3 is 65%.

[0156] - Precipitated lithium carbonates have a chemical quality illustrated by Table 18.

[0157] Lithium recovery is preferably carried out at a temperature of around 9533. Table 18: Chemical quality of Ü2CO3 (%) ,22 - The precipitated lithium carbonates have a purity of around 98% calculated by subtracting the sum of the impurities from 100. An X-ray diffraction analysis confirms these results and indicates that the product obtained is in the form of lithium carbonates in accordance with the standard sheet JCPDS 22-1141 (Figure 9), no additional lines were identified by X-ray diffraction.

[0158] Figure 9: DRX characterization of lithium carbonates

[0159] The refined mesh parameters of the developed product are listed in the following table:

[0160] Table 19: Structural parameters of the produced lithium carbonates Ü2CO3 Bibliographic references Melin and colleagues, 2018

[0161] Nan Ding, WO-2020-092157-A1

[0162] Basudev Swain, « Recovery and Recycling of Lithium: A Review », Separation and Purification Technology 172 ( 2017) , pages 388 403

[0163] I.Akalay, I.Benzakour, H.Faqir, A.Kaddami, K.Ouzaouit, WO 2010,150038 Urbani Mark Daniel, Vines nicholas John, Johnson Gary donald, WO 2020 / 160615, Uwe Zangemeister-Wittke, Claudio Di Paolo, Dominique Christine Tschudi, Nicholas, Ronald Glover, Dimitri Peter Fitsialos, PCT: US 2021 / 040203

[0164] Joaquin Hidalgo Betanzos, Lourdes Yurramendi Sarasola, Amal Siriwardana, Carmen DEL RIO GAZTELURRUTIA, EP3950977A1 Alexandru SONOC, Jacob JESWIET, Ahmad GHAHREMAN, PCT / CA2021 / 050663 William McLaughlin, Terry Adams, US588463A

Claims

CLAIMS 1 - Process for the recovery of selected elements from the mixture comprising cobalt, nickel, manganese, lithium, graphite carbon, iron, aluminum and copper, said process is characterized in that it comprises the following steps: i) Dissolving the mixture comprising the elements cobalt, nickel, manganese, lithium and graphite carbon by acid attack in the presence of a reducing agent, the addition of the acid and the reducing agent is done simultaneously with controlled flow rates without heating ii) Solid / liquid separation by means of filtration of the solution obtained in step i) makes it possible to obtain a solution comprising the metal ions of cobalt, nickel, manganese and lithium and a residue "A" based on graphite carbon. iii) The solution obtained following step ii) undergoes purification by selective precipitation at a pH varying between 4.5 and 6.5 leading to the formation of a precipitate.iv) The solution obtained following step iii) undergoes separations by organic solvent leading to the obtaining of two solutions B and C v) Solution B comprises cobalt and manganese and solution C comprises nickel and lithium vi) Solution B undergoes a liquid / liquid separation by organic solvent leading to the formation of two solutions D and E vii) Solution D comprises cobalt and solution E comprises manganese viii) Solution C undergoes a selective separation by precipitation of nickel in the form of nickel hydroxides or nickel carbonates and / or their mixtures ix) Solid / liquid separation by filtration following step viii) leading to the formation of a solution F comprising lithium. x) Solution D obtained following step vii) comprising the cobalt undergoes electrolysis after concentration to obtain the cobalt cathode with 99.98% purity xi) Solution E obtained following step vii) comprising the manganese undergoes precipitation by Na2CO3 leading to the formation of manganese carbonates xii) Solution F comprising the lithium undergoes selective precipitation by Na2CO3 leading to the formation of lithium carbonates with a purity of 99% - Process according to claim 1 characterized in that said mixture comprises materials from end-of-life lithium-ion batteries: black masses and / or waste from the production of lithium-ion batteries - Process according to claims 1 to 2 characterized in that the mixture is a material comprising cobalt, nickel, manganese, lithium, copper, aluminum, iron, graphite carbon - Process according to claims 1 and 2 Characterized in that the reducing agent is selectedamong the agents: sodium sulfite and / or hydrogen peroxide - Process according to claims 1 to 3 characterized in that the reducing agent is hydrogen peroxide - Process according to claims 1 to 3 characterized in that the pH of step iv) is 6 - Process according to claims 1 to 4 characterized in that steps iv) and ix) are carried out by adding NaOH and / or Na2CO3 and / or their mixtures. - Process according to claims 1 to 5 characterized in that step xiii) is carried out at a temperature varying between 00'C and 10 O'C - Process according to claims 1 to 6 characterized in that step xiii) is carried out at a pH between 1 1 and 14 0 - Process according to claims 1 to 7 characterized in that the solvent used in step v) is a phosphinic solvent 1 - Process according to claims 1 to 8 characterized in that the solvent used in step vii) is a phosphonic solvent 2- Process according to claims 1 to 7 characterized in that step xi) is carried out ata pH varying between 2.4 and 3.2 and a current density between 200 A / m 2 and 260 A / m 2 13- Process according to claims 1 to 9 characterized in that the precipitate obtained following step ii) has a purity greater than 94% 14- Process according to claim 13 characterized in that the purity of the graphite carbon obtained following step ii) undergoes an acid wash to lead to obtaining graphite carbon of high purity greater than 98%. 15- Method according to any one of claims 1 to 10 characterized in that the elements to be recovered from materials from end-of-life lithium-ion batteries comprise cobalt, nickel, manganese, lithium and graphite carbon. - Cobalt is recovered in the form of cobalt cathode - Nickel is recovered in the form of nickel hydroxide and / or nickel carbonates - Lithium is recovered in the form of lithium carbonates - Graphite carbon 16- The process according to claims 1 to 14 characterized in that the recovery yield of the elements Co, Ni, Mn is greater than 95% 17- The process according to claims 1 to 14 characterized in that the recovery yield of Li in the form of Li2CO3 is greater than 65% 18- Method according to claims 1 to 15 characterized in that cobalt, nickel, manganese, lithium and graphite carbon could be used in the preparation of new active materials for lithium-ion batteries.

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