Systems and methods for extracting metal values from active materials in lithium-ion batteries
The carbon thermal extraction process addresses inefficiencies in existing lithium-ion battery recycling methods by using a modular system to separate and extract metallic valuables efficiently at lower temperatures, achieving high purity and reduced resource needs.
Patent Information
- Application Number
- JP2024543445
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2022-02-03
- Filing Date
- 2023-01-31
- Publication Date
- 2025-02-06
AI Technical Summary
Current methods for extracting valuables from lithium-ion batteries, such as wet and dry smelting, are inefficient and face operational and configuration complexities.
A carbon thermal extraction process using a separation module and an extraction module, including an inert vessel, furnace, quenching device, filtration mechanism, and wet magnetic separation device, to extract metallic valuables at lower temperatures through multiple chemical and mechanical processes.
The process efficiently separates and extracts lithium and other metals in high purity, minimizing resource requirements and operational complexities.
Smart Images
Figure 2025503923000001_ABST
Abstract
Description
[Technical field]
[0001] CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] Embodiments of the present specification claim priority to Indian provisional patent application filed on February 3, 2022, bearing number 202211005731 and entitled "SYSTEM AND METHOD FOR EXTRACTION OF METAL VALUES FROM ACTIVE MATERIAL OF LITHIUM-ION BATTERIES," the contents of which are incorporated herein by reference in their entirety.
[0002]
[0002] The present invention relates generally to lithium ion batteries. In particular, the present invention relates to systems and methods that enable recycling of lithium ion batteries. More particularly, the present invention relates to systems and methods for extracting metal values from the active material of lithium ion batteries. [Background technology]
[0003]
[0003] Safe disposal of used lithium ion batteries has become very important in recent years due to the large-scale production of lithium ion batteries to power various devices and appliances. Currently, safe disposal of used lithium ion batteries is not without challenges, mainly due to the presence of active materials in the used batteries.
[0004]
[0004] Current processes used to extract values from the active metals of lithium-ion batteries broadly fall into two categories, namely hydrometallurgy and pyrometallurgy. Hydrometallurgy involves the use of acids to leach the active materials and then solvent-solvent extraction to extract the values. Pyrometallurgy involves the use of electric arc furnaces and melting the active materials. Heavy metals sink while light metals form a slag, and are thus extracted. However, these processes are inefficient and have multiple operational and setup complexities and difficulties.
[0005]
[0005] Therefore, there is a need for an efficient method for extracting active materials from lithium ion batteries.
[0006]
[0006] The above mentioned shortcomings, drawbacks, and problems are addressed herein, which will be understood by reading and studying the following detailed description. Summary of the Invention [Problem to be solved by the invention]
[0007]
[0007] A primary object of the present invention is to provide a system and method for extracting metal values from the active material of a lithium ion battery.
[0008] It is yet another object of the present invention to provide a carbothermal extraction process in an industrial environment.
[0009] It is yet another object of the present invention to provide a process which utilizes lower temperatures and a new series of reactions not conventionally utilized in current extraction methods.
[0010] These and other objects and advantages of the present invention will become readily apparent from the following detailed description taken in conjunction with the accompanying drawings. [Means for solving the problem]
[0011] Various embodiments of the present invention provide a system and method for extracting metal values from active materials in lithium ion batteries. The system includes a separation module and an extraction module. The extraction module further includes an inert vessel, a furnace apparatus, a quenching apparatus, a filtration mechanism, and a wet magnetic separation apparatus.
[0012] According to one embodiment of the present invention, a separation module is provided. The batteries are subjected to multiple electrical, mechanical and chemical processes to produce a black mass containing the active materials of the batteries, such as NMC, LCO LMO and graphite, together with some unavoidable contaminants.
[0013] According to one embodiment of the present invention, the black mass is placed in an inert container with a lid. The inert container is then placed in a furnace (continuous or muffle type) and heated to a temperature of 800±100 degrees Celsius for 2-5 hours to promote the following reaction: Note that the black mass typically contains all the reactants in the amounts required to promote the reaction:
[0014]
[0014]
number
[0015] (Wherein, M=Co, Ni, etc.)
[0016] The material is quenched in cold water (preferably a 2% w / w CaOH solution) and then the solution is heated and stirred for several hours with constant addition of CaOH until saturation.
[0017]
[0017]
number
[0018] According to yet another alternative embodiment of the present invention, after quenching, the suspension in the closed vessel is maintained at a preset solid-liquid-gas (S / L / G) ratio and subjected to constant agitation under a pressure higher than atmospheric pressure. Separation of the solid and liquid substances as well as absorption of carbon dioxide gas are possible due to constant agitation under higher pressure in the closed vessel. The suspension is filtered under high pressure and then the solution / liquid is vaporized to obtain lithium values. The filtration residue is subjected to wet magnetic separation, the magnetic substances containing cobalt, nickel and several other elements in the form of non-magnetic agglomerates. The temperature of the carbothermal reduction step is adjusted to extract selective elements while the non-magnetic agglomerates are again processed to extract the different metals present therein.
[0019]
[0019] These and other aspects of the embodiments herein will be better appreciated and understood when considered in conjunction with the following description and the accompanying drawings. It should be understood, however, that the following description, while indicating preferred embodiments and numerous specific details thereof, is given by way of illustration and not by way of limitation. Many changes and modifications may be made within the scope of the embodiments herein without departing from the spirit thereof, and the embodiments herein include all such modifications.
[0020] Other objects, features and advantages will occur to those skilled in the art from the following description of the preferred embodiment and the accompanying drawings. [Brief description of the drawings]
[0021] [Figure 1] FIG. 1 illustrates a system for extracting active material from a lithium-ion battery, according to one embodiment of the present invention. [Diagram 2]
[0022] FIG. 1 illustrates SEM and XRD images of lithium after extraction from a lithium ion battery, according to one exemplary embodiment of the present invention. [Diagram 3]
[0023] FIG. 1 illustrates characterization results of magnetic and non-magnetic materials extracted from a lithium-ion battery, according to one exemplary embodiment of the present invention. [Figure 4]
[0024] FIG. 1 illustrates an XRD image of non-magnetic material extracted from a lithium ion battery upon subsequent purification according to one exemplary embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0022]
[0025] Certain features of the invention are shown in some drawings and not in others. This is done for convenience only, since each feature may be combined with any or all of the other features in accordance with the invention.
[0023]
[0026] In the following detailed description, reference is made to the accompanying drawings which form a part hereof, and in which are shown by way of illustration specific embodiments which may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the embodiments, it being understood that other modifications may be made without departing from the scope of the embodiments. Thus, the following detailed description should not be taken in a limiting sense.
[0024]
[0027] Various embodiments of the present invention provide a system and method for extracting metal values from active materials of lithium ion batteries. The system includes a separation module and an extraction module. The extraction module further includes an inert vessel, a furnace apparatus, a quenching apparatus, a filtration mechanism, and a wet magnetic separation apparatus. The separation module is designed to separate the active materials from the lithium ion batteries. The inert vessel is designed to house the black mass obtained from the separation module. The furnace apparatus is designed to maintain the black mass in the inert vessel at a number of different pre-set temperature ranges to facilitate removal of moisture from the black mass and to facilitate a number of chemical reactions in the inert vessel. The quenching apparatus allows for quenching of the active materials with cold water to facilitate the creation of a suspension. The wet magnetic separation apparatus facilitates the separation of magnetic and non-magnetic materials from the filtered material.
[0025]
[0028] According to one embodiment of the present invention, the inert container is preferably made of a material such as stainless steel (SS330). The black mass contained within the inert container includes the positive and negative active materials of the lithium ion battery, graphite, and several unavoidable contaminants.
[0026]
[0029] According to one embodiment of the present invention, the furnace apparatus is preferably a continuous furnace or a muffle furnace. The furnace is designed to maintain the inert vessel at a preset temperature range for several hours. The temperature of the furnace is adjusted depending on whether any optional elements are to be extracted from the black mass.
[0027]
[0030] According to one embodiment of the present invention, the filtration mechanism is a closed vessel designed to hold the suspension after quenching. The suspension contains lithium carbonate, metal, and carbon dioxide after the active material in the suspension is stirred in excess carbon during quenching. The suspension in the closed vessel is maintained at a preset solid-liquid (S / L) ratio and subjected to constant stirring under pressure higher than atmospheric pressure in a carbon dioxide environment. Separation of the solid and liquid materials and absorption of carbon dioxide gas are made possible by constant stirring under higher pressure in the closed vessel. The liquid is then separated under pressure and then vaporized to obtain and extract lithium values, and the filtration residue is subjected to wet magnetic separation.
[0028]
[0031] According to one embodiment of the present invention, the wet magnetic separation device contains cobalt and nickel as magnetic materials and a plurality of non-magnetic materials in the filtered material. When the proportion of cobalt and nickel is high in the non-magnetic materials, the filtered material is subjected to the extraction process again together with new active materials of the lithium-ion battery. Also, when the purity of the magnetic materials is considered to be low, it is further subjected to magnetic separation multiple times.
[0029]
[0032] According to one embodiment of the present invention, a method for extracting metal values from active materials of lithium ion batteries is provided. The method includes the steps of providing an inert container for black mass obtained from separation of active materials from lithium ion batteries, maintaining the black mass (material) and the inert container at a higher temperature by placing the inert container in a furnace device to remove moisture and promote reaction, quenching the material in cold water in a quenching device to create a suspension and stirring in a carbon dioxide atmosphere at high pressure, stirring the suspension in a filtering mechanism at high pressure and with a specific solid-liquid ratio to filter solid and liquid materials, evaporating the liquid material to extract lithium values, and subjecting the filtered residue to wet magnetic separation in a wet magnetic separation device for further separation of magnetic and non-magnetic materials.
[0030]
[0033] According to one embodiment of the present invention, a separation module is provided. The batteries are subjected to multiple electrical, mechanical, and chemical processes to yield a black mass containing the battery's active materials such as NMC, LCO LMO, and graphite, along with some unavoidable contaminants.
[0031]
[0034] According to one embodiment of the present invention, the black mass is placed in an inert container with a lid. The inert container is then placed in a furnace (continuous or muffle type) and heated to a temperature of 800±100 degrees Celsius for 2-5 hours to promote the following reaction. It is noted that the black mass typically contains all the reactants in the amounts required to promote the reaction.
[0032]
[0035]
number
[0033]
[0036] (In the formula, M=Co, Ni, etc.)
[0034]
[0037] The material is quenched in cold water (preferably a 2% W / W CaOH solution) and then the solution is heated and stirred for several hours with constant addition of CaOH until saturation.
[0035]
[0038]
number
[0036]
[0039] According to yet another alternative embodiment of the invention, after quenching, the suspension in the closed vessel is maintained at a preset solid-liquid-gas (S / L / G) ratio and subjected to constant agitation at a pressure higher than atmospheric pressure. Separation of the solid and liquid substances as well as absorption of carbon dioxide gas are possible due to constant agitation at higher pressure in the closed vessel. The suspension is filtered under high pressure and then the solution / liquid is vaporized to obtain and extract the lithium values. The filtration residue is subjected to wet magnetic separation, the magnetic substances containing cobalt, nickel and several other elements in the form of non-magnetic agglomerates. The temperature of the carbothermal reduction step is adjusted to extract selective elements while the non-magnetic agglomerates are again processed to extract the different metals present therein.
[0037]
[0040] According to one exemplary embodiment of the present invention, experimental conditions and results of extraction of metal values from active materials of lithium-ion batteries are provided. A 500 kg batch of black lump material was placed in a furnace inside an austenitic stainless steel vessel and heated to temperatures of 300 degrees Celsius for 6 hours, 850 degrees Celsius for 2 hours, and 400 degrees Celsius for 30 minutes. The black lump material was then quenched and stirred in a pressure vessel at a pressure of 12 bar by constantly supplying a pure carbon dioxide gas environment with a S / L ratio of 1:3 until the pressure stabilized. Figure 2 illustrates SEM and XRD images of lithium after extraction from a lithium-ion battery, illustrating the evidence of extraction of high-quality lithium. The filtrate was then subjected to wet magnetic separation, and magnetic and non-magnetic materials were separated, as illustrated in Figures 3 and 4. To increase the purity and remove impurities, the magnetic materials were processed through a wet magnetic separator.
[0038]
[0041] 1 illustrates a system for extracting metal values from active materials in lithium-ion batteries. The system includes a separation module 101 and an extraction module 102. The extraction module further includes an inert vessel 102a, a furnace device 102b, a quenching device 102c, a filtration mechanism 102d, and a wet magnetic separation device 102e.
[0039]
[0042] FIG. 2 illustrates SEM and XRD images of lithium after extraction from a lithium ion battery according to one exemplary embodiment of the present invention.
[0040]
[0043] FIG. 3 illustrates characterization results of magnetic and non-magnetic materials extracted from a lithium-ion battery according to one exemplary embodiment of the present invention.
[0041]
[0044] FIG. 4 illustrates an XRD image of non-magnetic material extracted from a lithium-ion battery upon subsequent purification according to one exemplary embodiment of the present invention.
[0042]
[0045] Although the embodiments herein are described with reference to various specific embodiments, it will be apparent to those skilled in the art that they may practice the embodiments herein with modifications.
[0043] Effect of the Invention
[0046] Various embodiments of the present invention provide systems and methods for extracting metal values from the active material of lithium ion batteries. The extraction process extracts the metals in metallic form and the lithium directly in lithium carbonate or oxide form, which minimizes additional requirements or processing and therefore minimizes resources needed for setup and operational purposes.
[0044]
[0047] The foregoing description of the specific embodiments has so fully revealed the general nature of the embodiments herein, which can be easily modified and / or adapted for various applications, such as specific embodiments, by applying current knowledge without departing from the generic concept, and such adaptations and modifications are therefore intended to be understood within the meaning and range of equivalents of the disclosed embodiments. It should be understood that the expressions or terms used herein are for the purpose of description, not limitation. Thus, although the embodiments herein have been described in terms of preferred embodiments, those skilled in the art shall recognize that the embodiments herein can be practiced with modifications. However, all such modifications are deemed to be within the scope of the claims.
Claims
1. 1. A system for extracting metal values from active material of a lithium ion battery, comprising: a separation module designed to separate active material from the lithium ion battery; an inert container designed to contain the black mass obtained from the separation module; a furnace apparatus designed to maintain the black mass within the inert vessel at a plurality of different pre-set temperature ranges to facilitate removal of moisture from the black mass and to facilitate a plurality of chemical reactions within the inert vessel; a quenching device that allows the active material to be quenched with cold water to facilitate the preparation of a suspension; A filtration mechanism; and a wet magnetic separation device that facilitates separation of magnetic and non-magnetic materials from the filtered material.
2. 2. The system of claim 1, wherein the inert container is preferably made of a material such as stainless steel (SS330), and the black mass contained in the inert container includes positive and negative active materials of a lithium ion battery, graphite, and a number of unavoidable contaminants.
3. 2. The system of claim 1, wherein the furnace apparatus is preferably a continuous furnace or a muffle furnace, the furnace designed to maintain the inert vessel at a pre-set temperature range for several hours, the temperature of the furnace being adjusted depending on whether any optional elements are to be extracted from the black mass.
4. 2. The system of claim 1, wherein the filtration mechanism is a sealed vessel designed to hold the suspension after the quenching, the suspension comprising lithium carbonate, metal, and carbon dioxide after the active material in the suspension is agitated in excess carbon during quenching, the suspension in the sealed vessel is maintained at a preset solid-liquid (S / L) ratio and subjected to constant agitation under higher than atmospheric pressure in a carbon dioxide environment, separation of solid and liquid materials and absorption of carbon dioxide gas is enabled by the constant agitation under higher pressure in the sealed vessel, the liquid is then separated under pressure and subsequently vaporized to obtain and extract lithium values, and the filtration residue is subjected to wet magnetic separation.
5. 2. The system of claim 1, wherein the wet magnetic separation device contains cobalt and nickel as magnetic materials and a plurality of non-magnetic materials in the filtered material, and when the proportion of cobalt and nickel is high in the non-magnetic materials, the filtered material is subjected to the extraction process once more together with new active materials of a lithium ion battery, and when the purity of the magnetic materials is considered to be low, it is further subjected to magnetic separation multiple times.
6. 1. A method for extracting metal values from active materials of a lithium ion battery, comprising: providing an inert container for the black mass obtained from the separation of active material from the lithium ion battery; maintaining the black mass and the inert container at a higher temperature by placing the inert container in a furnace apparatus to remove moisture and promote reaction; quenching the material in cold water in a quencher to create a suspension and stirring in a carbon dioxide atmosphere at high pressure; agitating the suspension in a filtration mechanism at high pressure and a specific solid-to-liquid ratio to filter solid and liquid materials; evaporating the liquid material to extract lithium values; and subjecting the filtration residue to wet magnetic separation in a wet magnetic separation device for further separation of magnetic and non-magnetic materials.
7. 7. The method of claim 6, wherein the furnace apparatus is designed to maintain the inert vessel at a preset temperature range for several hours, and the temperature of the furnace is adjusted depending on whether any optional elements are extracted from the black mass.
8. 7. The method of claim 6, wherein the filtration mechanism is a sealed vessel designed to hold the suspension after the quenching, the suspension including lithium carbonate, metal, and carbon dioxide after the active material reacts with excess carbon during quenching, the suspension in the sealed vessel is maintained at a preset solid-liquid (S / L) ratio and subjected to constant agitation at a pressure higher than atmospheric pressure, and separation of solid and liquid materials and absorption of carbon dioxide gas is enabled by the constant agitation at the higher pressure in the sealed vessel.
9. 7. The method of claim 6, wherein the wet magnetic separation device facilitates separation of magnetic and non-magnetic materials from the filtered material, the wet magnetic separation device includes cobalt and nickel as magnetic materials and a plurality of non-magnetic materials in the filtered material, and when the proportion of cobalt and nickel is high, the filtered material is subjected to another extraction process together with new active material for a lithium ion battery.