Lithium extraction process from materials containing lithium and at least one other metal

Abstract

The present invention is in the field of lithium extraction from materials containing lithium and at least another metal. In particular, the present invention relates to a method for extracting lithium from materials containing at least lithium and at least another metal.

Description

[Technical Field]

[0001] The present invention relates to the field of lithium extraction from materials containing lithium and at least another metal. In particular, the present invention relates to a method for extracting at least lithium from materials containing lithium and at least another metal. [Background technology]

[0002] Lithium and its compounds have several industrial applications, including heat-resistant glass and ceramics, lithium grease lubricants, flux additives for iron, steel, and aluminum manufacturing, and lithium batteries and lithium-ion batteries, with the latter two being particularly important for the automotive industry. These uses account for more than three-quarters of lithium production.

[0003] Lithium-ion batteries are currently undergoing significant development due to their energy potential, manufacturing process, and low cost. These batteries are used in electronic devices, but most often in electric vehicles.

[0004] In particular, electric vehicles could account for 35% to 50% of all vehicle sales by 2040, and as a result, changes in lithium consumption will follow the same trend as the proliferation of electric vehicles. Therefore, according to recent research by ADEME and IFPen, the total demand for lithium by 2050 is estimated to be approximately 14 million tons per year.

[0005] Lithium salts can be extracted from water in mineral springs, brine pools, and brine deposits. Currently, brine extraction is probably the most widely used lithium extraction technology. However, at least two problems associated with lithium brine production have emerged, namely reliability problems and geographical problems. In fact, the impact of weather on the production of lithium brine operations is obvious, and as the global demand for lithium increases, a more reliable and consistent production method is needed. However, lithium brine operations are limited to selected climates and regions that can maintain sufficient weather to ensure economic processing.

[0006] Hard rock lithium deposits are geographically distributed more uniformly across the globe and are less dependent on climate for production, so they can meet demand.

[0007] Lithium exists in a variety of minerals and ores, but there are relatively few ores that contain sufficient amounts of lithium to be attractive and commercially viable lithium sources that are readily available. Among these commercially viable lithium sources, spodumene is the most interesting mineral, and various processes have been proposed to recover lithium values from spodumene ores. Only two methods, the sintering method and the sulfuric acid method, seem to be industrially implemented, and the sulfuric acid method has become the main method for producing lithium carbonate from spodumene due to its high efficiency. However, this process has inherent drawbacks such as high levels of sulfate and heavy metal ions in the product and a sophisticated process for recovering sodium sulfate.

[0008] Other methods include a leaching process with carbon dioxide in addition to an autoclave-based process. Due to the need for additional processes and the management of gaseous CO2, it is an economically and environmentally expensive process.

[0009] In addition, the evaluation of waste of electrical and electronic equipment (WEEE), also known as "urban mines," has become a topic of interest as it represents an important potential source of lithium.

[0010] In fact, given the increasing demand for lithium, policies that manage recycled materials can provide the resources necessary for growth to countries that lack access to (or do not directly utilize) raw materials.

[0011] Furthermore, the European Union is beginning to take this issue into consideration, as evidenced by the numerous directives adopted in its Action Plan for Recycling, Ecodesign and the Circular Economy of WEEE. In the specific case of batteries, this recycling is regulated by Directive 2006 / 66 / EC of the European Parliament and the Council of 6 September 2006 on Batteries and Storage Batteries and Waste Batteries and Storage Batteries, which, in Article 13, states that "Member States shall encourage the development of new recycling and processing technologies and promote research into environmentally friendly and cost-effective recycling methods for batteries and storage batteries of all kinds."

[0012] Several recycling processes exist for lithium-ion batteries, most of which are based on either wet or dry smelting. Wet smelting processes use strong acid baths, are highly solvent-intensive, and result in high economic and environmental costs. Furthermore, the use of strong acids for leaching non-selectively dissolves all active electrode components (i.e., lithium, and other metals such as Co, Ni, and Mn). This implies the need for several additional extraction and / or precipitation steps.

[0013] Wet smelting requires high heating of compounds (700-1000°C or higher) to extract them, which requires a lot of energy and also comes with high economic and environmental costs.

[0014] Some processes use concentrated eutectic solvents for recycling the positive electrode of lithium-ion batteries. However, these processes still involve the complete dissolution of elements present in the positive electrode material, such as Co, Ni, and / or Mn in addition to Li. Therefore, a selective precipitation treatment is necessary to isolate Li from other metals.

[0015] Other methods include heating in water in the presence of oxidizing agents such as hydrogen peroxide and carbon dioxide, or using volatile organic solvents and acids. However, the need for additional steps, the management of gaseous CO2 or organic solvents, and the handling and subsequent disposal of oxidizing agents or acids make these processes expensive from an economic and environmental standpoint. [Overview of the Initiative]

[0016] Therefore, an object of the present invention is to provide an economically viable process, in particular one that uses little energy and is environmentally friendly, that does not require the use of hazardous chemicals and / or chemicals that require waste post-treatment.

[0017] A further object of the present invention is to provide a method for easily separating lithium from other metals in the case of extraction of a lithium source containing other metals.

[0018] Therefore, in one aspect, the present invention relates to a process for extracting at least lithium from a material comprising lithium and at least another metal, wherein the process is a) A step of contacting the material with a polyol solvent and a carbonate to obtain a reaction mixture, b) A step of obtaining a solvothermal-treated composition SP1 by subjecting the reaction mixture obtained in step a) to solvothermal treatment. c) A step of separating the liquid L1 containing lithium carbonate and the solid S1 that form the composition SP1 obtained in step b), d) Optionally, a step to isolate solid lithium carbonate from liquid L1. Includes.

[0019] The present invention also relates to a process for extracting at least lithium from a material comprising lithium and at least another metal, wherein the process is: a) A step of contacting the material with a polyol solvent and a carbonate to obtain a reaction mixture, b) A step of obtaining a solvothermal-treated composition SP1 by subjecting the reaction mixture obtained in step a) to solvothermal treatment. c) A step of separating the liquid L1 containing lithium carbonate and the solid S1 that form the composition SP1 obtained in step b), d) Optionally, a step to isolate solid lithium carbonate from liquid L1. e) A step of bringing solid S1 into contact with water to obtain composition SP2, f) A step of separating the liquid L2 containing lithium carbonate and the solid S2 that form the composition SP2 obtained in step e), g) Optionally, a step to isolate solid lithium carbonate from liquid L2. Includes.

[0020] In certain embodiments, the solid S2 comprises at least another metal.

[0021] In certain embodiments, at least another metal is selected from transition metals and post-transition metals, and in particular from Co, Ni, Mn, Fe, Ti, and Al, and in particular from Co, Ni, Mn, and Al.

[0022] In certain embodiments, the material includes, or is, a lithium-ion battery cathode material selected from the following: - Lithium and cobalt-containing lithium-ion battery cathode materials, especially LiCoO2, - Lithium and manganese-containing lithium-ion battery cathode materials, especially LiMn2O4, - Lithium-ion battery cathode materials containing lithium, nickel, manganese, and cobalt, especially LiNi 0.33 Mn 0.33 Co 0.33 O2, - Lithium, nickel, cobalt, and aluminum-containing lithium-ion battery cathode materials, particularly LiNi 0.8 Co 0.15 Al 0.05 O2, - Lithium and titanium-containing lithium-ion battery cathode materials, particularly Li4Ti5O 12 , - Lithium and iron-containing lithium-ion battery cathode materials, particularly Li3Fe2(PO4)3, - A mixture of at least two of the materials listed above.

[0023] In certain embodiments, the material comprises, or is, a lithium-ion battery cathode material selected particularly from: - Lithium and cobalt-containing lithium-ion battery cathode materials, particularly LiCoO2, - Lithium and manganese-containing lithium-ion battery cathode materials, particularly LiMn2O4, - Lithium, nickel, manganese, and cobalt-containing lithium-ion battery cathode materials, particularly LiNi 0.33 Mn 0.33 Co 0.33 O2, - Lithium, nickel, cobalt, and aluminum-containing lithium-ion battery cathode materials, particularly LiNi 0.8 Co 0.15 Al 0.05 O2, and, - A mixture of at least two of the materials listed above.

[0024] In more specific embodiments, the lithium-ion battery cathode material is a mixture cathode material is a mixture of two, three, four or more of the above materials. For example, a mixture consisting of, or containing, LiCoO2, LiMn2O4, LiNi 0.33 Mn 0.33 Co 0.33 O2 and LiNi 0.8 Co 0.15 Al 0.05 O2 may be, or a mixture containing them may be.

[0025] In certain embodiments, the material is a material that includes the lithium-ion battery cathode material described above.

[0026] In certain embodiments, the material is the lithium-ion battery cathode material described above.

[0027] The material may also be the positive electrode of a lithium-ion battery.

[0028] The lithium-ion battery cathode material may be, for example, a spent cathode, manufacturing scrap, or unsuitable material. In particular, the lithium-ion battery cathode material may be a crushed spent cathode, a lithium-containing composition of a spent cathode, or aluminum foil coated with a lithium composition found in a spent lithium-ion battery cathode.

[0029] The material may also be a lithium-ion battery. In particular, the lithium-ion battery anode does not interfere with the process of the present invention.

[0030] Lithium-ion batteries are, for example, used batteries, manufacturing scrap, or unsuitable materials. In particular, lithium-ion batteries may be crushed used batteries or lithium-containing compositions of used batteries.

[0031] In certain embodiments, the material is lithium ore, particularly sialite (more specifically LiAlSi2O6), feldspar (more specifically LiAlSi4O6) 10 ), lithium mica (more specifically, K(Li,Al)3(Si,Al)4O 10 (F,OH)2), eucryptite (more specifically LiAlSiO4), amblygonite (more specifically (Li,Na)AlPO4(F,OH)), or mixtures thereof.

[0032] If the lithium ore material is stearate, the stearate is preferably calcined before step a). This calcination is known to those skilled in the art and makes it possible to convert α-stearate to β-stearate.

[0033] In certain embodiments, the material is in powder form. More specifically, the material is in the form of a composition comprising a plurality of particles having a size in the range of 1 to 1000 μm, particularly 1 to 100 μm.

[0034] When the material is a lithium-ion battery cathode material, the material is usually already in powder form within the lithium-ion battery cathode.

[0035] If the material is lithium ore, it may be pulverized into powder form as described above before step a).

[0036] In certain embodiments, the polyol solvent is selected from the group comprising ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylenediol, liquid polyethylene glycol such as polyethylene glycol 200-600, butylene glycol, particularly 1,3-butylene glycol and 1,4-butylene glycol, hexylene glycol, and glycerol.

[0037] In certain embodiments, the polyol solvent is anhydrous. Anhydrous means, in particular, that the polyol solvent contains 5% or less by weight of water, especially 4% or less, 3% or less, 2% or less, 1% or less, 0.5% or less, 0.4% or less, 0.3% or less, 0.2% or less, or 0.1% or less, more specifically 1% or less by weight of water.

[0038] In certain embodiments, the carbonate is at least one metal carbonate, particularly at least one alkali metal carbonate, more specifically sodium carbonate, potassium carbonate, or a mixture thereof.

[0039] In more specific embodiments, the carbonate is sodium carbonate and / or potassium carbonate, and more specifically, sodium carbonate or potassium carbonate.

[0040] In certain embodiments, the mass concentration of the material in the polyol solvent is in the range of 1 to 100 g / L, particularly 5 to 50 g / L, and more specifically 10 to 20 g / L, for example, about 16 g / L.

[0041] In certain embodiments, the weight ratio of the material to the carbonate is in the range of 0.1 to 10, particularly 0.2 to 5. In certain embodiments, the process is carried out in the absence of acids, particularly strong acids such as hydrochloric acid, nitric acid, or sulfuric acid; in the absence of carbon dioxide; in the absence of oxidizing agents, particularly hydrogen peroxide, ozone, or persulfates; and in the absence of volatile organic solvents such as acetone, acetonitrile, benzene, 1-butanol, acetic acid, chloroform, t-butanol, cyclohexane, carbon tetrachloride, ethyl acetate, dimethyl sulfoxide, dichloromethane, ethanol, diethyl ether, isopropyl acetate, heptane, dichloroethane, 2-propanol, isooctane, diisopropyl ether, 1-propanol, methylcyclohexane, dimethylformamide, ethyl acetate, 2-methyl THF, dioxane, methyl t-butyl ether, dimethyl acetate, methanol, toluene, dimethoxyethane, methyl ethyl ketone, tetrahydrofuran, hexane, xylene, N-methylpyrrolidinone, pentane, and pyridine.

[0042] The contact step a) can be carried out in accordance with any technique known to those skilled in the art, in particular by mechanical, magnetic or manual stirring and / or ultrasonic treatment.

[0043] In a particular embodiment, the polyol solvent is used in the extraction step prior to the present invention. c This corresponds to liquid L1 of ). This embodiment corresponds to the recycling of the polyol solvent used in the framework of the present invention. This recycling can be performed two, three, four or more times. In this case, the polyol solvent is particularly used in the nth extraction step according to the present invention using the polyol solvent. c This corresponds to liquid L1, and this polyol solvent is obtained in particular from the (n-1)th extraction using the polyol solvent, and the polyol solvent used in the (n-1)th extraction is, for example, from the (n-2)th extraction step c) is liquid L1, etc.

[0044] The solvothermal treatment in step b) can be carried out in accordance with any technique known to those skilled in the art, in particular by using an autoclave, more specifically a stainless steel autoclave.

[0045] The autoclave may be configured in a batch, semi-batch, or continuous configuration. Such configurations are known to those skilled in the art.

[0046] In certain embodiments, the solvothermal treatment in step b) is carried out at a temperature above the boiling point of the polyol solvent but below 500°C.

[0047] In a particular embodiment, the solvothermal treatment of step b) is carried out at a temperature of 200 to 500°C, particularly 220 to 500°C, more specifically 220 to 400°C, for example, about 225°C.

[0048] In certain embodiments, the solvothermal treatment in step b) is carried out at a pressure above atmospheric pressure, for example, above 1.013 bar, and below 5000 bar, particularly in the range of 10 to 500 bar, more specifically about 125 bar.

[0049] In certain embodiments, the solvothermal treatment in step b) is carried out for 1 hour to 1 week, particularly 2 hours to 5 days, and more specifically 4 to 80 hours, especially when the autoclave is in a batch configuration.

[0050] In certain embodiments, the solvothermal treatment in step b) is performed for 0.25 to 24 hours, particularly 0.5 to 10 hours, especially when the autoclave is in a continuous configuration.

[0051] The separation step c) can be carried out according to any technique known to those skilled in the art, particularly by centrifugation, filtration and / or decantation, and more specifically by centrifugation.

[0052] Step d) can be carried out according to any technique known to those skilled in the art, particularly by evaporation of the polyol solvent, and more specifically under reduced pressure.

[0053] In an advantageous embodiment, the solid S1 obtained in step c) is washed with a solvent in which lithium carbonate does not dissolve before step e). This solvent is selected in particular from alcohol solvents, such as ethanol or propanol, and ketone solvents, such as acetone. For example, this washing can be carried out by contacting the solid S1 with ethanol under ultrasonic conditions, and then the washed solid S1 is separated from the liquid, in particular by centrifugation.

[0054] The contact step e) can be carried out in accordance with any technique known to those skilled in the art, in particular by mechanical, magnetic or manual stirring and / or ultrasonic treatment.

[0055] The separation step f) can be carried out according to any technique known to those skilled in the art, particularly by centrifugation, filtration and / or decantation, and more specifically by centrifugation.

[0056] In a particular embodiment, if at least another metal is at least a magnetic metal, or at least a magnetic metal and at least a non-magnetic metal, the separation step f) includes a magnetic separation sub-step f1) for isolating at least the magnetic metal from composition SP1, followed by a separation sub-step f2) corresponding to the separation step f) described above, to obtain a liquid L2 and a solid S2 containing at least the non-magnetic metal in particular.

[0057] Step g) can be carried out in accordance with any technique known to those skilled in the art, particularly by evaporation of water, and more specifically under reduced pressure.

[0058] Solid S2 can be further dried and / or calcined according to any technique known to those skilled in the art.

[0059] In more specific embodiments, the present invention relates to a process for extracting lithium and cobalt from lithium- and cobalt-containing lithium-ion battery cathode materials, particularly from or comprising LiCoO2, wherein the process is: a) A step of contacting the material with a polyol solvent and a carbonate to obtain a reaction mixture, b) A step of obtaining a solvothermal-treated composition SP1 by subjecting the reaction mixture obtained in step a) to solvothermal treatment. c) A step of separating the liquid L1 containing lithium carbonate and the solid S1 that form the composition SP1 obtained in step b), d) Optionally, a step to isolate solid lithium carbonate from liquid L1. e) A step of bringing solid S1 into contact with water to obtain composition SP2, f) A step of separating the liquid L2 containing lithium carbonate and the solid S2 containing cobalt that form composition SP2 obtained in step e), g) Optionally, a step to isolate solid lithium carbonate from liquid L2. Includes.

[0060] In more specific embodiments, the present invention relates to lithium, nickel, manganese, and cobalt-containing lithium-ion battery cathode materials, particularly LiNi 0.33 Mn 0.33 Co 0.33 The process relates to the extraction of lithium and cobalt from a material consisting of or containing O2, and the process is as follows: a) A step of contacting the material with a polyol solvent and a carbonate to obtain a reaction mixture, b) A step of obtaining a solvothermal-treated composition SP1 by subjecting the reaction mixture obtained in step a) to solvothermal treatment. c) A step of separating the liquid L1 containing lithium carbonate and the solid S1 that form the composition SP1 obtained in step b), d) Optionally, a step to isolate solid lithium carbonate from liquid L1. e) A step of bringing solid S1 into contact with water to obtain composition SP2, f1) A step of magnetically separating composition SP2 to isolate the solids containing cobalt and nickel from the composition. f2) A step of separating the liquid L2 containing lithium carbonate and the solid S2 containing manganese in particular in the form of MnCO3, which form the composition obtained at the end of step f1. g) Optionally, a step to isolate solid lithium carbonate from liquid L2. Includes.

[0061] In more specific embodiments, the present invention relates to an extraction process for lithium and manganese-containing lithium-ion battery cathode materials, particularly LiMn2O4, wherein the process is a) A step of contacting the material with a polyol solvent and a carbonate to obtain a reaction mixture, b) A step of obtaining a solvothermal-treated composition SP1 by subjecting the reaction mixture obtained in step a) to solvothermal treatment. c) A step of separating the liquid L1 containing lithium carbonate and the solid S1 that form the composition SP1 obtained in step b), d) Optionally, a step to isolate solid lithium carbonate from liquid L1. e) A step of bringing solid S1 into contact with water to obtain composition SP2, f) A step of separating the liquid L2 containing lithium carbonate and the solid S2 containing manganese in particular the form of MnCO3 and / or Mn3O4, which form composition SP2 obtained in step e), g) Optionally, a step to isolate solid lithium carbonate from liquid L2. h) Optionally, a step of calcining solid S2 to obtain solid S3 containing manganese in particular the form of Mn2O3, Includes.

[0062] In more specific embodiments, the present invention relates to lithium, nickel, cobalt, and aluminum-containing lithium-ion battery cathode materials, particularly LiNi 0.8 Co 0.15 Al 0.05 Regarding the O2 extraction process, the process is as follows: a) A step of contacting the material with a polyol solvent and a carbonate to obtain a reaction mixture, b) A step of obtaining a solvothermal-treated composition SP1 by subjecting the reaction mixture obtained in step a) to solvothermal treatment. c) A step of separating the liquid L1 containing lithium carbonate and the solid S1 that form the composition SP1 obtained in step b), d) Optionally, a step to isolate solid lithium carbonate from liquid L1. e) A step of bringing solid S1 into contact with water to obtain composition SP2, f1) A step of magnetically separating composition SP2 to isolate the solids containing cobalt and nickel from the composition. f2) A step of separating the liquid L2 containing lithium carbonate and the solid S2 containing aluminum in particular CoAlO and / or CoAlO form, which form the composition obtained at the end of step f1. g) Optionally, a step to isolate solid lithium carbonate from liquid L2. Includes.

[0063] In another embodiment, the present invention relates to a lithium-ion battery cathode recycling process, which includes the above-mentioned steps, after recovering lithium-ion battery cathode material from a lithium-ion battery or lithium-ion battery, and optionally further includes a step after the above-mentioned steps of using at least one of the above-mentioned metals in a new process or device.

[0064] In another embodiment, the present invention is - Materials selected from lithium-ion battery cathode materials and lithium ore, -Carbonates, and -Polyol solvent, This relates to compositions containing the following:

[0065] In particular, the composition is a composition for solvothermal treatment.

[0066] It should be noted that all of the embodiments described above in relation to the process also apply to this embodiment.

[0067] In certain embodiments, the material is lithium ore or a lithium-ion battery cathode material selected from the following: - Lithium and cobalt-containing lithium-ion battery cathode materials, especially LiCoO2, - Lithium and manganese-containing lithium-ion battery cathode materials, especially LiMn2O4, - Lithium-ion battery cathode materials containing lithium, nickel, manganese, and cobalt, especially LiNi 0.33 Mn 0.33 Co 0.33 O2, - Lithium-ion battery cathode materials containing lithium, nickel, cobalt, and aluminum, especially LiNi 0.8 Co 0.15 Al 0.05 O2, - Lithium and titanium-containing lithium-ion battery cathode materials, especially Li4Ti5O 12 , -Optionally, Li3Fe2(PO4)3 and, - A mixture of at least two of the materials listed above.

[0068] In certain embodiments, the material is lithium ore or a lithium-ion battery cathode material selected from the following: - Lithium and cobalt-containing lithium-ion battery cathode materials, especially LiCoO2, - Lithium and manganese-containing lithium-ion battery cathode materials, especially LiMn2O4, - Lithium-ion battery cathode materials containing lithium, nickel, manganese, and cobalt, especially LiNi 0.33 Mn 0.33 Co 0.33 O2, - Lithium-ion battery cathode materials containing lithium, nickel, cobalt, and aluminum, especially LiNi 0.8 Co 0.15 Al 0.05 O2, and - A mixture of at least two of the materials listed above.

[0069] In another aspect, the present invention relates to a composition SP1 obtained by the method described above, wherein the material is selected particularly from lithium-ion battery cathode material and lithium ore.

[0070] In certain embodiments, the material is lithium ore or a lithium-ion battery cathode material selected from the following: - Lithium and cobalt-containing lithium-ion battery cathode materials, especially LiCoO2, - Lithium and manganese-containing lithium-ion battery cathode materials, especially LiMn2O4, - Lithium-ion battery cathode materials containing lithium, nickel, manganese, and cobalt, especially LiNi 0.33 Mn 0.33 Co 0.33 O2, - Lithium-ion battery cathode materials containing lithium, nickel, cobalt, and aluminum, especially LiNi 0.8 Co 0.15 Al 0.05 O2, - Lithium and titanium-containing lithium-ion battery cathode materials, especially Li4Ti5O 12 , -Optionally, Li3Fe2(PO4)3 and, - A mixture of at least two of the materials listed above.

[0071] In certain embodiments, the material is lithium ore or a lithium-ion battery cathode material selected from the following: - Lithium and cobalt-containing lithium-ion battery cathode materials, especially LiCoO2, - Lithium and manganese-containing lithium-ion battery cathode materials, especially LiMn2O4, - Lithium-ion battery cathode materials containing lithium, nickel, manganese, and cobalt, especially LiNi 0.33 Mn 0.33 Co 0.33 O2, - Lithium-ion battery cathode materials containing lithium, nickel, cobalt, and aluminum, especially LiNi 0.8 Co 0.15 Al 0.05O2, and - A mixture of at least two of the materials listed above.

[0072] In another embodiment, the present invention relates to a composition comprising a polyol solvent (particularly ethylene glycol) and a solid composition, wherein the polyol solvent comprises lithium, and the solid composition comprises lithium carbonate and cobalt (particularly cobalt α and / or cobalt β).

[0073] In another embodiment, the present invention relates to a composition comprising a polyol solvent (particularly ethylene glycol) and a solid composition, wherein the polyol solvent comprises lithium, and the solid composition comprises lithium carbonate, nickel and cobalt (particularly in the form of a Ni-Co alloy), and manganese carbonate.

[0074] In another embodiment, the present invention relates to a composition comprising a polyol solvent (particularly ethylene glycol) and a solid composition, wherein the polyol solvent comprises lithium, and the solid composition comprises lithium carbonate, manganese carbonate, and manganese oxide (particularly Mn3O4). It should be noted that all embodiments described above in relation to the process also apply in this embodiment.

[0075] definition The following terms and expressions included in b are defined as follows:

[0076] As used herein, a range of values ​​in the form of "xy" or "x~y" includes integers x, y, and integers in between. For example, the statement "1~6" or "1~6 (1 to 6)" or "1~6 (1 through 6)" is intended to include integers 1, 2, 3, 4, 5, and 6. Preferred embodiments include each individual integer within the range, as well as any partial combination of integers. For example, preferred integers in "1~6" may include 1, 2, 3, 4, 5, 6, 1~2, 1~3, 1~4, 1~5, 2~3, 2~4, 2~5, 2~6, and so on.

[0077] As used herein, the term "about" refers specifically to a range of values ​​within ±10% of a particular value. For example, the term "about 100" includes values ​​of 100 ± 10%, i.e., values ​​between 90 and 110.

[0078] "Sorvothermal processing" specifically refers to a process in a closed reaction vessel in which decomposition or chemical reactions are induced between precursors in the presence of a solvent at a temperature higher than the boiling point of the solvent. The pressure may be automatic or applied, and is particularly automatic.

[0079] "Compounds insoluble in solvents" specifically refers to compounds whose solubility in the solvent at a temperature of 25°C is 1 g / L or less, more specifically, 0.1 g / L or less. [Modes for carrying out the invention]

[0080] Examples

[0081] Example 1: Extraction of lithium and other metals according to the present invention from lithium-ion battery cathode material

[0082] The extraction of lithium and other metals from lithium-ion battery cathode materials according to the present invention is carried out, for example, as follows.

[0083] Step 1: This process is carried out in a solvothermal container, such as a steel or titanium container, in the presence of ethylene glycol or diethylene glycol and sodium carbonate and / or potassium carbonate. After dissolving the carbonate in the solvent, lithium-ion battery cathode material (in powder form) is added. The materials tested were LiCoO2, LiMn2O4, and LiNi 0.33 Mn 0.33 Co 0.33 O2 and Li3Fe2(PO4)3, and LiNi 0.8 Co 0.15 Al 0.05The solution was O2. Next, the container was closed and introduced into the heating chamber. Examples of processing conditions for different battery materials are summarized in Table 1. The pressure inside the container is 125 bar, and can be higher if achievable by the selected container.

[0084] TIFF0007891210000001.tif43170

[0085] At the end of this stage, the container, after cooling to room temperature, contains the powder suspended in the liquid. The liquid L1 and powder S1 are separated by centrifugation. Next, the recovered powder S1 is subjected to the following process.

[0086] Step 2: The powder S1 recovered in step 1 may be washed with ethanol. The powder is brought into contact with ethanol under ultrasonic conditions for several minutes, and then separated from the liquid by centrifugation. The purpose of this washing is to remove residual sodium carbonate and ethylene glycol.

[0087] Step 3: Next, the powder obtained in step 1 or 2 is washed with water to obtain a solid S2 suspended in an aqueous liquid L2. The solid S2 is recovered and then dried at 90°C for up to 2 hours. LiRing 0.33 Mn 0.33 Co 0.33 In the case of O2, since magnetic separation follows washing, step 3 is slightly modified (step 3') to place the powder dispersed in water near a magnet to separate the magnetic and non-magnetic fractions of the powder. In practice, only one of the phases formed during the process (nickel-cobalt alloy) is magnetic and therefore attracted by the magnet. Next, the supernatant liquid L2 is subjected to the processing in the following step.

[0088] Step 4: Dry liquid L2 in air at 90°C for 3-5 hours.

[0089] The powder obtained after steps 3 and 4 may, if necessary, be used in the final step.

[0090] Step 5: Bake at 500 or 800°C for 2 hours in air.

[0091] The compositions of solid S2 and liquid L2 for several materials are shown in Table 2 below.

[0092] TIFF0007891210000002.tif34170

[0093] The extraction yields for multiple materials are shown in Table 3 below.

[0094] TIFF0007891210000003.tif41170

[0095] It was found that the extraction yield of metals (Co, Ni, Mn) recovered in powder form could be improved by reusing the polyol solvent and aqueous solution (i.e., by using the L1 and / or L2 liquids from the previous process).

[0096] Example 2: Extraction of lithium from lithium ore

[0097] It has been shown that a process similar to that described in Example 1 can be successfully carried out for lithium ores such as sialite. For example, 1.0 g of βLiAlSi2O6 was successfully treated with 0.85 g of Na2CO3 in 30 ml of EG at 225°C for 12 hours. EG solvent can be reused as described above.

[0098] Example 3: Extraction of lithium and other metals by reusing polyol solvents

[0099] Ethylene glycol solvent (EG) can be reused at least four times without filtration. The reused EG retains its reducing properties.

[0100] LiMn 2 O 4 About electrode powder The same solvent and processing conditions were used to perform the procedure twice as described below. 0.5 g of LiMn2O4 was treated with 0.2 g of K2CO3 in 30 ml of EG at 225°C for 5 hours. The obtained SP1 composition was analyzed by inductively coupled plasma (ICP). The results are shown in Table 4 below.

[0101] TIFF0007891210000004.tif58170

[0102] The yield of Mn can generally be increased, for example, by increasing the centrifugation rate. From the second use of the solvent, the yield of recovered Li and / or Mn in the S1 powder can be close to or exceed 100% because residual material (Mn oxide particles) or dissolved material (Li carbonate) is recovered in the EG derived from the first use.

[0103] LiMn 2 O 4 Regarding electrode powder (double quantity) The following three procedures were performed using the same solvent and under the same processing conditions. 1.0 g of LiMn2O4 was treated with 0.2 g of K2CO3 in 30 ml of EG at 225°C for 8 hours. The obtained SP1 composition was analyzed by inductively coupled plasma (ICP). The results are shown in Table 5 below.

[0104] TIFF0007891210000005.tif62170

[0105] The yield of Mn can generally be increased, for example, by increasing the centrifugation rate. From the second use of the solvent, the yield of recovered Li and / or Mn in the S1 powder can be close to or exceed 100% because residual material (Mn oxide particles) or dissolved material (Li carbonate) is recovered in the EG derived from the first use.

[0106] Example 4: Extraction of lithium and other metals from a mixture of electrode powders (LiCoO2, LiMn2O4, LiNi 0.33 Mn 0.33 Co 0.33 O2, LiLiLi 0.8 Co 0.15 Al 0.05 O2)

[0107] The following four experiments were conducted using the same solvent and under the same processing conditions. 0.25g LiCool 2. 0.25g NMC, 0.25g NCA and 0.25g LiMn 2 O A 1.0 g mixture containing 4 was treated with 1.52 g of K2CO3 in 60 ml of EG at 225°C for 45 hours.

[0108] The obtained SP1 composition was analyzed by inductively coupled plasma (ICP). The results are shown in Table 6 below.

[0109] TIFF0007891210000006.tif107170

[0110] The three powders are as follows: - A powder obtained from S2, which is attracted by magnets and essentially contains Ni-Co alloy, -A free powder obtained from S2, which essentially contains MnCO3. -A powder obtained from L2, containing pure Li2CO3, after drying the supernatant.

[0111] Example 4 demonstrates that even when electrode powders are mixed, the separation of the desired elements can still be achieved.

[0112] Therefore, the method of the present invention makes it possible to recycle a mixture of battery powders without going through a sorting step. Furthermore, the purity of the recovered compound is preserved by reusing the same solvent several times.

[0113] Example 5: Regarding the entire battery

[0114] After disassembling the MI battery, powder was recovered from the electrodes (a mixture of negative and positive electrodes). The collected powder was sieved using the following three different mesh sieves: -To obtain the powder hereafter referred to as "MI T630", 630 μm, -To obtain the powder hereafter referred to as "MI T200", 200 μm, - 40 μm to obtain the powder hereafter referred to as "MI T40". MI T200 powder was analyzed by inductively coupled plasma (ICP). The results are shown in Table 7 below.

[0115] TIFF0007891210000007.tif25170

[0116] 1.0 g of MI T200 powder was treated with 30 ml of EG containing 0.5 g of K2CO3 at 225°C for 8 hours. The obtained SP1 composition was analyzed by inductively coupled plasma (ICP). The results are shown in Table 7 below.

[0117] TIFF0007891210000008.tif44170

[0118] Lithium carbonate can be separated from Al by sieving. Lithium carbonate can also be redissolved in water, filtered, and the solution dried to separate it from aluminum. This process can replace centrifugation. The powder attracted by the magnet (from the S2 solid) essentially contains CoO, α- and β-Co. 1.0 g of MI T40 powder was treated with 0.5 g of K2CO3 in 30 ml of EG (already used once) at 225°C for 16 hours.

[0119] From the obtained SP1 and then S2 solids, the powder attracted by the magnet essentially contained α- and β-Co, and the free fraction could be sieved to recover only graphite. Lithium carbonate can be separated from Al by sieving. Lithium carbonate can also be redissolved in water, filtered, and the solution dried to separate it from aluminum. This process can replace centrifugation. Most of the graphite remains on the 200-micron sieve, and the majority on the 630-micron sieve, and in either case, it is not affected by the recycling process.

Claims

1. A process for extracting at least lithium from a material containing lithium and at least another metal, a) A step of contacting the material with a polyol solvent and sodium carbonate and / or potassium carbonate to obtain a reaction mixture, b) The reaction mixture obtained in step a) is subjected to solvothermal treatment to obtain a solvothermal-treated composition SP1, c) A step of separating the liquid L1 containing lithium carbonate and the solid S1 that form the composition SP1 obtained in step b), A process that includes this.

2. a) A step of contacting the material with a polyol solvent and sodium carbonate and / or potassium carbonate to obtain a reaction mixture, b) The reaction mixture obtained in step a) is subjected to solvothermal treatment to obtain a solvothermal-treated composition SP1, c) A liquid L1 containing lithium carbonate that forms composition SP1 obtained in step b) A step to separate the solid S1, e) A step of bringing the solid S1 into contact with water to obtain composition SP2, f) A step of separating the liquid L2 containing lithium carbonate and the solid S2 that form the composition SP2 obtained in step e), The process according to claim 1, including the process described in claim 1.

3. After step c), d) A step comprising isolating solid lithium carbonate from liquid L1, The process according to claim 2.

4. After step f), g) A step of isolating solid lithium carbonate from liquid L2, The process according to claim 2 or 3.

5. The process according to any one of claims 1 to 4, wherein the at least other metal is selected from transition metals and post-transition metals.

6. The process according to any one of claims 1 to 5, wherein the at least other metal is Mn.

7. The process according to any one of claims 1 to 6, wherein the material is a lithium-ion battery cathode material.

8. The process according to any one of claims 1 to 7, wherein the material is lithium ore.

9. The process according to any one of claims 1 to 8, wherein the polyol solvent is selected from the group comprising ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylenediol, liquid polyethylene glycol, butylene glycol, hexylene glycol, and glycerol.

10. The process according to any one of claims 1 to 9, wherein the polyol solvent corresponds to the liquid L1 in step c) of claim 1.

11. The process according to any one of claims 1 to 10, wherein the solvothermal treatment in step b) is carried out at a temperature above the boiling point of the polyol solvent and below 500°C.

12. The process according to any one of claims 1 to 11, wherein the solvothermal treatment in step b) is performed at a pressure higher than atmospheric pressure and at a pressure of 5,000 bar (5 × 10⁸ Pascals) or less.

13. The process according to any one of claims 1 to 12, wherein the solvothermal treatment in step b) is performed for 1 hour to 1 week.

14. The process according to any one of claims 2 to 13, wherein the solid S1 obtained in step c) is washed with a solvent in which lithium carbonate does not dissolve before step e).

15. The product according to claim 2, wherein the at least other metal is at least a magnetic metal, or at least a magnetic metal and at least a non-magnetic metal, and step f) includes a magnetic separation sub-step f1) for isolating the at least magnetic metal from the composition SP2, and a separation sub-step f2) for separating the liquid L2 containing lithium carbonate from the solid S2. Rothes.

16. A lithium-ion battery cathode recycling process comprising the step according to claim 1 or 2, after the step of recovering lithium-ion battery cathode material from a lithium-ion battery.

17. - Materials selected from lithium-ion battery cathode materials and lithium ore, - Sodium carbonate and / or potassium carbonate, - Polyol solvent, A composition containing the following:

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