Method for recovering valuable metals from used lithium-ion secondary batteries

Abstract

The present invention relates to a method for recovering valuable metals from used lithium-ion secondary batteries using a CO2 / CO / H2O gas mixture or CH4 / air, or solid carbon, or a combination thereof.

Description

[Technical field]

[0001] The present invention relates to a method for recovering valuable metals from used lithium ion secondary batteries. [Background technology]

[0002] Energy storage devices, especially rechargeable batteries such as lithium-ion secondary batteries (LIBs), are in high demand for home appliances and electric vehicles. LIBs are important because they have become the most common power source for portable electronic devices. As their capacity and charging speed improve, LIBs are being used in a variety of applications.

[0003] This growing demand has significantly boosted the production of LIBs, which in turn has led to a significant increase in the amount of used LIBs. These used LIBs need to be treated through appropriate processes. Therefore, efforts are underway to recover battery components while minimizing environmental pollution.

[0004] It is usually not easy to recover valuable metals (such as cobalt, lithium, nickel, manganese, copper, aluminum, and iron) from LIBs at a high recovery rate.

[0005] Therefore, there is a need for an efficient method to recover valuable metals from used LIBs. Recycling used LIBs promotes environmental protection and promotes a circular economy by separating valuable metal components from other products. Summary of the Invention [Means for solving the problem]

[0006] In one embodiment, the present invention provides a method for recovering valuable metals from a used lithium ion secondary battery, the method comprising: (a) opening a lithium-ion secondary battery (LIB) and removing the cover; (b) crushing the remaining used lithium ion secondary batteries at a predetermined temperature to obtain particulate used lithium ion secondary batteries including particles having a predetermined particle size; (c) separating any plastic and Teflon matrix from the particulate spent lithium ion secondary battery material; (d) subjecting the separated particulate spent lithium ion secondary battery material to a CO2 / CO / H2O gas mixture, a CH4 / air gas mixture, or solid carbon, or a combination thereof, to carbonize the lithium, to obtain the particulate spent lithium ion secondary battery material containing lithium carbonate. acid a step of treating the material at a predetermined temperature to cure the material; (e) treating the particulate spent lithium ion secondary battery material comprising lithium carbonate with cold water and, optionally, further with CO2; (f) filtering the slurry obtained in step (e) to obtain a lithium carbonate filtrate and a residue containing cobalt, iron, other valuable metals, and non-metallic impurities; (g) heating the lithium carbonate filtrate at a predetermined temperature to obtain a lithium carbonate precipitate and a mother liquor by filtration after precipitating the lithium carbonate precipitate; (h) treating the residue containing cobalt, iron, other value metals and non-metallic impurities of step (f) with a flux at a predetermined temperature to obtain a value metal ingot. [Brief description of the drawings]

[0007] The subject matter which is regarded as the invention is particularly pointed out and distinctly claimed in the concluding portion of the specification, however the invention, together with its objects, features and advantages, both as to organization and method of operation, may best be understood by reference to the following detailed description taken in conjunction with the accompanying drawings.

[0008] [Figure 1] FIG. 1 is a schematic diagram showing a method for recovering valuable metals from used lithium ion secondary batteries. [Diagram 2] FIG. 1 is a schematic diagram showing one embodiment of the system (laboratory setup) of the present invention: 1. furnace with temperature controller, 2. reaction chamber (Pyrex), 3. sample or sample containing solid carbon, 4. CO2 cylinder, 5. gas washing bottle, 6. gas sampler for GC analysis, 7. thermocouple, 8. additional temperature monitor, 9. flow meter, 10. valve, 11. CO2 cylinder, 12. water vapor generator, 13. CH4 cylinder.

[0009] It will be appreciated that for simplicity and clarity of illustration, elements illustrated in the figures have not necessarily been drawn to scale. For example, dimensions of some elements may be shown exaggerated relative to other elements for clarity. Further, where appropriate, the same reference numerals may be repeated among the figures to indicate corresponding or similar elements. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] In the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, those skilled in the art will appreciate that the present invention may be practiced without these specific details. In other instances, well-known methods, procedures, and components have not been described in detail so as not to obscure the present invention.

[0011] In one embodiment, the present invention is a method for recovering valuable metals from used lithium ion secondary batteries, the method comprising: (a) opening the lithium ion secondary battery and removing the cover; (b) crushing the remaining used lithium ion secondary batteries at a predetermined temperature to obtain particulate used lithium ion secondary batteries including particles having a predetermined particle size; (c) separating any plastic and Teflon matrix from the particulate spent lithium ion secondary battery material; (d) subjecting the separated particulate spent lithium ion secondary battery material to a CO2 / CO / H2O gas mixture, a CH4 / air gas mixture, or solid carbon, or a combination thereof, to carbonize the lithium, to obtain the particulate spent lithium ion secondary battery material containing lithium carbonate. acid a step of treating the material at a predetermined temperature to cure the material; (e) treating the particulate spent lithium ion secondary battery material comprising lithium carbonate with cold water and, optionally, further with CO2; (f) filtering the slurry obtained in step (e) to obtain a lithium carbonate filtrate and a residue containing cobalt, iron, other valuable metals, and non-metallic impurities; (g) heating the lithium carbonate filtrate at a predetermined temperature to precipitate a lithium carbonate precipitate and obtain a lithium carbonate precipitate and a mother liquor by filtration; (h) treating the residue containing cobalt, iron, other valuable metals and non-metallic impurities of step (f) with a flux at a predetermined temperature to obtain a valuable metal ingot.

[0012] In one embodiment, the “spent LIB” is made up of mainly metal shells, membrane separators, and cathode materials (LiCoO2, LiMn2O4, LiFePO4, Li4Ti5O 12 , LiNi 0.3 Al 0.3 Co 0.3 The present invention refers to used / discarded lithium ion secondary batteries containing lithium ion (Li2CO3, Co, TiO2, Cu, alumina, iron oxide, sodium oxide, calcium oxide, etc.), aluminium foil, anode material (graphite), copper foil and organic electrolyte. The present invention provides a method for recovering and / or recycling valuable metals from lithium ion secondary batteries. Such valuable metals may include cobalt, nickel, manganese, copper, aluminium, iron, titanium, tin, lead, zinc, sodium, and calcium. Non-limiting examples of valuable metals obtainable by the method and system of the present invention include Li2CO3, Co, TiO2, Cu, alumina, iron oxide, sodium oxide, and calcium oxide.

[0013] As used herein, "other valuable metals" refers to at least one of nickel, manganese, copper, aluminum, titanium, tin, lead, zinc, sodium or calcium.

[0014] Valuable metals can be obtained as metal ingots and used as materials for other products.

[0015] In one embodiment, a method for recovering valuable metals from a spent lithium ion secondary battery includes opening the lithium ion secondary battery, removing the battery coating layer or shell, and removing the exposed gas. The remaining spent LIBs are further used in the method of the present invention.

[0016] De-sealing of the LIBs is performed by any known technique in the art, such as those described in Zheng X. A Mini-Review on Metal Recycling from Spent Lithium Ion Batteries. Engineering, 2018, 4, 3, 361-370, and Meshram P. Extraction of lithium from primary and secondary sources by pre-treatment, leaching and separation, A comprehensive review, Hydrometallurgy, 2014, 150, 12, 192-208, which are incorporated herein by reference.

[0017] In some embodiments, the method of the present invention includes a step of crushing the remaining used lithium ion secondary batteries (LIBs) at a predetermined temperature to obtain particulate used lithium ion secondary battery material. In other embodiments, the predetermined temperature employed in the crushing step is 20-50° C. In other embodiments, the particulate used lithium ion secondary battery material has a particle size of 2-10 mm. In other embodiments, it has a particle size of 2-5 mm. In other embodiments, it has a particle size of 4-10 mm.

[0018] In some embodiments, the method of the present invention includes a step of separating any plastic and Teflon matrix from the particulate spent lithium ion secondary battery material. In other embodiments, the separation is performed by air, which is based on the different gravitational forces of the materials. In other embodiments, the separation is performed by any other method known in the art, such as described in Peukert W. Industrial separation of fine particles with difficult dust properties, Powder Technology, 2001, 118, 1-2, 8, 136-148, which is incorporated herein by reference.

[0019] In one embodiment, the present invention provides a method for recovering valuable metals from spent lithium ion secondary batteries, the method comprising: acid The method includes treating the separated particulate lithium ion secondary battery material with a CO2 / CO / H2O gas mixture, a CH4 / air gas mixture, solid carbon, or a combination thereof at a predetermined temperature to oxidize the lithium ion secondary battery material. As used herein, CO2 / CO / H2O gas mixture refers to a gas mixture of CO2(g), CO(g) and H2O(g). 4 / Air gas mixture refers to a mixture of CH4 and air or gas in the presence of oxygen.

[0020] In some embodiments, the method of the present invention comprises decomposing the separated particulate spent lithium ion secondary battery material into carbon dioxide to obtain a particulate spent lithium ion secondary battery material comprising lithium carbonate. acidThe method includes treating the carbon black with a CO2 / CO / H2O gas mixture, a CH4 / air gas mixture, solid carbon, or a combination thereof at a predetermined temperature to oxidize the carbon black. In another embodiment, the carbon black is treated at a temperature between 100 and 900°C. In another embodiment, the carbon black is treated at a temperature between 100 and 300°C. In another embodiment, the carbon black is treated at a temperature between 100 and 200°C. In another embodiment, the carbon black is treated at a temperature between 150 and 300°C. In another embodiment, the carbon black is treated at a temperature between 150 and 250°C. In another embodiment, the carbon black is treated at a temperature between 100 and 500°C. In another embodiment, the carbon black is treated at a temperature between 600 and 900°C. In another embodiment, the carbon black is treated at a temperature between 200 and 800°C. In another embodiment, the carbon black is treated at a temperature between 100 and 700°C. In another embodiment, the carbon black is treated at a temperature between 650 and 850°C. In another embodiment, the carbon black is treated at a temperature between 700 and 900°C. In another embodiment, the carbon black is treated at a temperature between 600 and 700°C. In another embodiment, the carbon black is treated at a temperature between 700 and 800°C. In another embodiment, the treatment is carried out at a temperature of 800 to 900°C.

[0021] In some embodiments, the method of the present invention comprises the step of: removing lithium from a carbon dioxide gas to obtain a particulate spent lithium ion secondary battery material comprising lithium carbonate. acid The method includes treating the separated particulate used lithium ion secondary battery material with a CO2 / CO / H2O gas mixture at a predetermined temperature to oxidize the separated particulate used lithium ion secondary battery material. In another embodiment, the treatment is performed at a temperature between 100 and 300°C. In another embodiment, the treatment is performed at a temperature between 100 and 200°C. In another embodiment, the treatment is performed at a temperature between 150 and 300°C. In another embodiment, the treatment is performed at a temperature between 150 and 250°C.

[0022] In some embodiments, the method of the present invention comprises: separating the separated particulate spent lithium ion secondary battery material from the lithium carbonate to obtain a particulate spent lithium ion secondary battery material comprising lithium carbonate. acidThe method includes treating the mixture with a CH4 / air gas mixture at a predetermined temperature to oxidize the oxidized carbon dioxide. In another embodiment, the temperature is between 100 and 900°C. In another embodiment, the temperature is between 100 and 300°C. In another embodiment, the temperature is between 100 and 200°C. In another embodiment, the temperature is between 150 and 300°C. In another embodiment, the temperature is between 150 and 250°C. In another embodiment, the temperature is between 100 and 500°C. In another embodiment, the temperature is between 600 and 900°C. In another embodiment, the temperature is between 200 and 800°C. In another embodiment, the temperature is between 100 and 700°C. In another embodiment, the temperature is between 650 and 850°C. In another embodiment, the temperature is between 700 and 900°C. In another embodiment, the temperature is between 600 and 700°C. In another embodiment, the temperature is between 700 and 800°C. In another embodiment, the temperature is between 800 and 900°C.

[0023] In some embodiments, the method of the present invention comprises the step of: converting lithium into carbon to obtain particulate spent lithium ion secondary battery material comprising lithium carbonate. acid The method includes treating the particulate used lithium ion secondary battery material separated using solid carbon at a predetermined temperature to oxidize the particulate used lithium ion secondary battery material. In another embodiment, the treatment is performed at a temperature of 600-900°C. In another embodiment, the treatment is performed at a temperature of 650-850°C. In another embodiment, the treatment is performed at a temperature of 700-900°C. In another embodiment, the treatment is performed at a temperature of 600-700°C. In another embodiment, the treatment is performed at a temperature of 700-800°C. In another embodiment, the treatment is performed at a temperature of 800-900°C.

[0024] In some embodiments, the CO2 / CO partial pressure of the CO2 / CO / H2O gas mixture used in the methods and systems of this invention is 0.1-100. In other embodiments, the CO2 / CO partial pressure is 0.1-20. In other embodiments, the CO2 / CO partial pressure is 0.1-30. In other embodiments, the CO2 / CO partial pressure is 10-50. In other embodiments, the CO2 / CO partial pressure is 1-30. In other embodiments, the CO2 / CO partial pressure is 50-100. In other embodiments, the CO2 / CO partial pressure is 30-100.

[0025] In some embodiments, the partial pressure of H2O in the CO2 / CO / H2O mixture used in the methods and systems of the present invention is between 0.1% and 50% v / v. In other embodiments, the partial pressure of H2O is between 10% and 50% v / v. In other embodiments, the partial pressure of H2O is between 1% and 30% v / v. In other embodiments, the partial pressure of H2O is between 20% and 50% v / v. In other embodiments, the partial pressure of H2O is between 0.1% and 10% v / v.

[0026] In some embodiments, the partial pressure of CH4 in the CH4 / air gas mixture used in the methods and systems of the present invention is between 0.1% and 100% v / v. In other embodiments, the partial pressure of CH4 is between 0.1% and 50% v / v. In other embodiments, the partial pressure of CH4 is between 10% and 50% v / v. In other embodiments, the partial pressure of CH4 is between 1% and 30% v / v. In other embodiments, the partial pressure of CH4 is between 20% and 50% v / v. In other embodiments, the partial pressure of CH4 is between 0.1% and 10% v / v. In other embodiments, the partial pressure of CH4 is between 30% and 100% v / v. In other embodiments, the partial pressure of CH4 is between 50% and 100% v / v.

[0027] In some embodiments, the weight ratio of the carbon to the separated particulate used lithium ion secondary battery material used in the method and system of the present invention is 10:100 to 200:100. In other embodiments, the weight ratio of the carbon to the separated particulate used lithium ion secondary battery material is 50:100 to 200:100. In other embodiments, the weight ratio of the carbon to the separated particulate used lithium ion secondary battery material is 100:100 to 200:100. In other embodiments, the weight ratio of the carbon to the separated particulate used lithium ion secondary battery material is 150:100 to 200:100. In other embodiments, the weight ratio of the carbon to the separated particulate used lithium ion secondary battery material is 10:100 to 100:100. In other embodiments, the weight ratio of the carbon to the separated particulate used lithium ion secondary battery material is 50:100 to 150:100. In another embodiment, the weight ratio of the carbon to the separated particulate used lithium ion secondary battery material is 50:100 to 100:100. In another embodiment, the weight ratio of the carbon to the separated particulate used lithium ion secondary battery material is 70:100 to 100:100. In another embodiment, the weight ratio of the carbon to the separated particulate used lithium ion secondary battery material is 50:100 to 80:100.

[0028] In some embodiments, the methods and systems of the present invention provide lithium extraction. In other embodiments, the yield of lithium extraction is between 85-100%. In other embodiments, the yield is between 90-100%.

[0029] In some embodiments, the methods and systems of the present invention comprising treatment with a CH4 / air gas mixture provide lithium extraction, while in other embodiments the yield of lithium extraction is between 90-100%.

[0030] In some embodiments, the methods and systems of the present invention, including treatment with a CO2 / CO2 / H2O mixture, provide lithium extraction, and in other embodiments, the yield of lithium extraction is 90-100%.

[0031] In some embodiments, the methods and systems of the present invention using solid carbon provide lithium extraction, while in other embodiments, the yield of lithium extraction is between 90-100%.

[0032] In some embodiments, the methods and systems of the present invention using solid carbon provide for non-ferrous metal extraction. In other embodiments, the yield of non-ferrous metal extraction is 99% or greater. In other embodiments, the yield of non-ferrous metal extraction is 99.2% or greater.

[0033] In some embodiments, the solid carbon used in the methods and systems of the present invention for recovering valuable metals from spent lithium ion secondary batteries comprises coal, coke, charcoal, graphite, or any combination thereof.

[0034] In another embodiment, the solid carbon is coal. In another embodiment, the solid carbon is coke. In another embodiment, the solid carbon is charcoal. In another embodiment, the solid carbon is graphite.

[0035] In some embodiments, after treatment with the CO2 / CO / H2O mixture, the particulate spent lithium ion secondary battery material containing lithium carbonate is treated with cold water and then further treated with CO2. In some embodiments, after treatment with the CO2 / CO / H2O mixture, the particulate spent lithium ion secondary battery material containing lithium carbonate is treated with cold water only.

[0036] In some embodiments, after treatment with solid carbon, the particulate spent lithium ion secondary battery material comprising lithium carbonate is treated with cold water.

[0037] The solubility of Li2CO3 in cold water is low. For example, the solubility of Li2CO3 at 25°C is much higher than that of d-metals, at 12.9 gm / L, compared to 0.093 gm / L for NiCO3. On the other hand, the solubility of Li2CO3 drops to 6.9 gm / L at 100°C.

[0038] In some embodiments, the separated particulate spent lithium ion secondary battery material is treated with a CO2 / CO / H2O mixture or a CH4 / air mixture at a predetermined temperature to produce carbon dioxide. acid A polymerization reaction occurs, and particulate used lithium ion secondary battery material containing lithium carbonate is obtained.

[0039] Charcoal acid The reaction can be as follows:

[0040] [ka]

[0041] In some embodiments, the separated particulate spent lithium ion secondary battery material is treated with solid carbon at a predetermined temperature to produce carbon. acid A polymerization reaction occurs, and particulate used lithium ion secondary battery material containing lithium carbonate is obtained.

[0042] Charcoal when using solid carbon acid The reaction can be as follows:

[0043] [ka]

[0044] Treatment with cold water (after treatment with CO2 / CO / H2O, CH4 / air or solid carbon) produces a slurry which is filtered to produce a lithium carbonate filtrate and a residue containing cobalt, iron, other valuable metals, and non-metallic impurities. In some embodiments, the other valuable metals include nickel, manganese, copper, aluminum (i.e., alumina), iron (i.e., iron oxide), titanium, tin, lead, zinc, sodium (i.e., sodium oxide), calcium (i.e., calcium oxide), or combinations thereof. In other embodiments, the aluminum is alumina. In other embodiments, the iron is iron oxide. In other embodiments, the sodium is sodium oxide. In other embodiments, the calcium is calcium oxide.

[0045] In other embodiments, the non-metallic impurities include organic binders, hard carbon, plastic casings, polymer foils and electrolytes, silica, or combinations thereof.

[0046] In some embodiments, the lithium carbonate filtrate is heated at a predetermined temperature to obtain a precipitate having lithium carbonate deposited thereon, and then filtered to obtain a lithium carbonate precipitate and a mother liquor.

[0047] In another embodiment, the lithium carbonate filtrate is heated to 80-120°C. In another embodiment, the lithium carbonate filtrate is heated to 80-100°C. In another embodiment, the lithium carbonate filtrate is heated to 80-90°C. In another embodiment, the lithium carbonate filtrate is heated to 90-120°C. In another embodiment, the lithium carbonate filtrate is heated to 100-120°C.

[0048] In some embodiments, the lithium carbonate precipitate is further dried to obtain a dried lithium carbonate powder. In other embodiments, the lithium carbonate precipitate or lithium carbonate powder prepared by the method of the present invention is further used as a material in the fields of ceramics, glasses and batteries.

[0049] Lithium carbonate is used in the manufacture of ceramics, glasses, and lithium-ion secondary batteries. It is a common ingredient in both low-fire and high-fire ceramic glazes. It forms low-melting fluxes with materials such as silica. Glasses derived from lithium carbonate are useful for ovenware.

[0050] In some embodiments, the residue obtained after filtration of the slurry, containing cobalt, iron, other valuable metals, and non-metallic impurities, is treated with a flux at a predetermined temperature to smelt the valuable metals to obtain a metal ingot, hi other embodiments, the flux comprises silica, carbon, calcium oxide, sodium oxide, alumina, iron oxide, or combinations thereof.

[0051] A flux is a chemical cleaning, fluidizing, or refining agent. Fluxes are used in both extractive metallurgy and metal joining.

[0052] During the smelting process, flux is added to the contents of the smelting furnace or cupola to remove chemical impurities from the metal and to make the slag more liquid at melting temperatures. Slag is a liquid mixture of ash, flux, and other impurities.

[0053] The role of flux is twofold: first, to dissolve oxides on the metal surface and make it easier to bond to the metal, and second, to coat the hot metal surface and prevent oxidation by oxygen.

[0054] In other embodiments, the metal ingot is comprised of ferrous or non-ferrous metals including cobalt, nickel, manganese, copper, aluminum, titanium, tin, lead, zinc, sodium, calcium, and combinations thereof.

[0055] In another embodiment, the aluminum is alumina, in another embodiment, the sodium is sodium oxide, in another embodiment, the calcium is calcium oxide.

[0056] In another embodiment, the treatment with the flux is carried out at a temperature of 1200-1500°C. In another embodiment, the treatment with the flux is carried out at a temperature of 1200-1300°C. In another embodiment, the treatment with the flux is carried out at a temperature of 1300-1400°C. In another embodiment, the treatment with the flux is carried out at a temperature of 1300-1500°C. In another embodiment, the treatment with the flux is carried out at a temperature of 1400-1500°C.

[0057] In some embodiments, the metal ingots prepared by the methods of the present invention are used as materials in metal production and as dopants in various alloys.

[0058] In other embodiments herein, "metal ingot" includes / refers to non-ferrous metal or ferrous ingots selected from cobalt, nickel, manganese, copper, aluminum (i.e., alumina), titanium, tin, lead, zinc, sodium (i.e., sodium oxide), calcium (calcium oxide), and combinations thereof. In other embodiments, the aluminum is alumina. In other embodiments, the sodium is sodium oxide. In other embodiments, the calcium is calcium oxide.

[0059] In some embodiments, the present invention provides a system for recovering valuable metals from used lithium ion secondary batteries, the system comprising: a reaction chamber containing a sample, a furnace for heating the sample, and a CO2 cylinder, a CO cylinder, a water vapor generator, and / or a CH4 cylinder, the sample comprising the separated particulate used lithium ion secondary battery material as described in the method of the present invention, characterized in that CO2, CO, and water vapor or CH4 are supplied to the reaction chamber to obtain the particulate used lithium ion secondary battery material.

[0060] In some embodiments, the present invention provides a system for recovering valuable metals from used lithium ion secondary batteries, the system comprising: a reaction chamber containing solid carbon and a sample, and a furnace for heating the sample, the sample comprising the separated particulate used lithium ion secondary battery material described in the method of the present invention, characterized in that the solid carbon and the sample are heated at a temperature of 600-900°C to obtain the particulate used lithium ion secondary battery material comprising lithium carbon.

[0061] In another embodiment, the system of the present invention includes a sample, the sample comprising particulate spent lithium ion secondary battery material. In another embodiment, the separated particulate spent lithium ion secondary battery material comprises particles having a predetermined particle size and is prepared by grinding spent LIBs at a predetermined temperature to obtain particulate spent lithium ion secondary battery material separated from any plastic and Teflon matrix from the particulate spent lithium ion secondary battery material.

[0062] In some embodiments, the system is shown in FIG.

[0063] FIG. 2 is a schematic diagram of a system according to some embodiments of the present invention. FIG. 2 is a schematic diagram of a system for use in recovering valuable metals from spent lithium-ion secondary batteries, showing, without limitation, a furnace with a temperature controller 1 in contact with a reaction chamber 2. The reaction chamber contains a sample 3 (and optionally solid carbon). The sample comprises particulate spent lithium-ion secondary battery material as described in the method of the present invention. The sample is treated with a CO2 / CO / H2O mixture, where a CO2 cylinder 4, a CO cylinder 11, a CH4 cylinder 14, and a water vapor generator 12 are connected to the reaction chamber, and the sample is supplied with a CO2 / CO / H2O or CH4 air mixture. The system further comprises a gas washing bottle 5 connected to the reaction chamber to neutralize the gas, a gas sampler 6 connected to the gas washing bottle 5 for GC analysis of the mixed gas, a thermocouple 7 attached to the sample to measure its temperature, an optional additional temperature monitor 8 attached to the sample to measure its temperature, flow meters 9 connected to the CO and CO2 cylinders used to determine their partial pressures, and valves 10 connected upstream of the flow meters 9 to the CO and CO2 cylinders to determine the gas flow.

[0064] The furnace with temperature controller 1 in contact with the reaction chamber 2 is configured to heat the reaction chamber to 100-900°C in the treatment with a CO2 / CO / H2O mixed gas. In another embodiment, it is configured to heat to 100-200°C. In another embodiment, it is configured to heat to 100-300°C. In another embodiment, it is configured to heat to 150-300°C. In another embodiment, it is configured to heat to 150-250°C. In another embodiment, the treatment with a CH4-air mixture and solid carbon is carried out at 600-900°C.

[0065] In some embodiments, the present invention provides a method for recovering valuable metals from used lithium ion secondary batteries by using the system of the present invention.

[0066] While the invention has been described in terms of a preferred embodiment, it will be appreciated by those skilled in the art to which the invention pertains that the conception upon which this disclosure is based may be readily utilized as a basis for the design of other structural systems and processes for carrying out the several purposes of the present invention.

[0067] example

[0068] Example 1

[0069] For lithium-containing components of lithium-ion secondary batteries, carbonization with CO2 / CO / H2O or CH4 / air gas mixtures or solid carbon acid A curing test and a cold water treatment of the obtained product were carried out. Exposure of the lithium-containing members of the lithium-ion secondary battery was carried out at 100 to 900°C.

[0070] material

[0071] The experiment involved the use of sodium titanate (Li4Ti5O 12 ), Lithium cobalt oxide (LiCoO2), Lithium phosphate (LiFePO4), Lithium nickel manganese cobalt oxide (Ni x Mn y Co z O2(x+y+z=1), Lithium Nickel Cobalt Aluminum Oxide Ni x Co y Al z A model mixture consisting of O2 (x+y+z=1) and lithium phosphate (Li3PO4) was used. These materials were used as positive or negative electrodes in various types of lithium-ion secondary batteries.

[0072] Experimental procedure

[0073] Charcoal of model mixtures using CO2 / CO / H2O or CH4 / air gas mixtures acid The curing was carried out in a laboratory furnace with a controlled temperature range of 100–900 °C. The test duration was 2 h. The laboratory setup is shown in Figure 2.

[0074] The powder of the model mixture was placed in a furnace or a quartz boat. Before heating, the quartz reactor was washed under a nitrogen flow of 100 mL / min, and then the furnace was heated at a predetermined temperature again under a nitrogen flow of 100 mL / min. After the reaction chamber reached a predetermined temperature, a CO2 / CO / H2O or CH4 / air gas mixture was fed into the reaction chamber. The above separated particulate used lithium-ion secondary battery materials were heated at a predetermined temperature with carbon. acid The chemical reactions that can occur during the conversion are as follows:

[0075] [ka]

[0076] After cooling under nitrogen flow, the Pyrex glass boat was removed from the furnace. The final product was weighed and treated with cold water. The treated slurry was then filtered. The filtrate was analyzed by ICP MS. The lithium balance for each test was calculated. From each lithium balance, the percentage of lithium extraction into the filtrate was evaluated.

[0077] result

[0078] The results are shown in Tables 1 and 2.

[0079] Table 1. Charcoal by CO2 / CO / H2O acid Chemical - Cold Water Treatment Test Results

[0080] [Table 1] TIFF0007636816000005.tif191170

[0081] Mixture 1 is 25% Li4Ti5O 12 , 25% LiCoO2, 25% LiFePO4, and 25% Li3PO4. Mixture 2 is 20% Li4Ti5O 12 , 40% LiCoO2, 20% LiFePO4, and 20% Li3PO4.

[0082] Table 2. Charcoal treated with CH4 and cold water acid Chemical test results

[0083] [Table 2]

[0084] Example 2

[0085] The solid carbon obtained by using the lithium-containing components of the lithium-ion secondary battery and the carbon obtained by cold water treatment acid Sintering tests were carried out. The lithium-containing components of the lithium-ion secondary battery were exposed to temperatures of 600 to 900°C. Below 600°C, the amount of extracted lithium and non-ferrous metals (cobalt, nickel) dropped sharply due to a drop in carbon reduction ability. When sintering was performed at temperatures above 900°C, the porosity of the material decreased, so the amount of extracted lithium and non-ferrous metals (cobalt, nickel) dropped sharply.

[0086] material

[0087] The experiments included lithium cobalt oxide (LiCoO2), lithium iron phosphate (LiFePO4), and nickel manganese cobalt oxide (LiNi x Mn y CozO2(x+y+z=1), Nickel Cobalt Aluminum Oxide LiNi x Co y Al z A model mixture of O2 (x+y+z=1) was used. These materials were used as positive and negative electrodes in various types of lithium-ion secondary batteries.

[0088] Experimental Procedure

[0089] Charring of model mixtures using solid carbon acid The curing was carried out in a temperature-controlled laboratory furnace at 600–900 °C. The test duration was 2 h. The laboratory setup is shown in Figure 2.

[0090] The powder of the model mixture containing solid carbon was placed in a furnace in an alumina boat. Before heating, the quartz reaction chamber was washed under a nitrogen flow of 100 mL / min, and then the furnace was heated at a predetermined temperature again under a nitrogen flow of 100 mL / min. After the reaction chamber reached a predetermined temperature, nitrogen was supplied to the reaction chamber. The separated particulate used lithium-ion secondary battery material was heated at a predetermined temperature to carbon. acid The chemical reactions that can occur during the conversion are as follows:

[0091] [ka]

[0092] After cooling under nitrogen flow, the alumina boat was removed from the furnace. The final product was weighed and treated with cold water. The treated slurry was then filtered. The filtrate and precipitate were analyzed using ICP MS. The percentages of lithium, cobalt, and nickel were calculated for each test. From each percentage, the extraction rate of lithium for the filtrate and the extraction rates of cobalt and nickel for the precipitate were evaluated.

[0093] result

[0094] The results are shown in Table 3. Table 3. Charcoal with fixed carbon and cold water treatment acid Chemical test results

[0095] [Table 3] TIFF0007636816000009.tif131170

[0096] While certain features of the invention have been illustrated and described herein, many modifications, substitutions, changes, and equivalents will occur to those skilled in the art, and it is therefore to be understood that the appended claims are intended to cover all such modifications and changes that fall within the true spirit of the invention.

Claims

1. A method for recovering valuable metals from used lithium ion secondary batteries, comprising: (a) opening the lithium ion secondary battery and removing the cover; (b) crushing the remaining used lithium ion secondary batteries at a certain temperature to obtain the used lithium ion secondary batteries in particulate form; (c) separating any plastic and Teflon matrix from the particulate spent lithium ion secondary battery material; (d) separating the particulate used lithium ion secondary battery material from the separated particulate used lithium ion secondary battery material by CH ４ , or C.H. ４ / air at a temperature that causes the lithium to carbonate; (e) treating the particulate used lithium ion secondary battery material containing lithium carbonate with cold water, and optionally with CO ２ and processing the result using (f) filtering the slurry obtained in step (e) to obtain a lithium carbonate filtrate and a residue containing cobalt, iron, other valuable metals and non-metallic impurities; (g) heating the lithium carbonate filtrate at a temperature to precipitate lithium carbonate precipitate, to obtain a lithium carbonate precipitate and a mother liquor by filtration; (h) treating the residue containing cobalt, iron, other value metals and non-metallic impurities of step (f) with a flux at a temperature to obtain a value metal ingot.

2. 2. The method of claim 1, wherein the particulate spent lithium ion secondary battery material obtained in step (b) has a particle size of 2 to 10 mm, or 2 to 5 mm.

3. The method of claim 1, wherein the temperature in step (b) when the remaining used lithium ion secondary batteries are pulverized to obtain particulate used lithium ion secondary battery material is 20 to 50° C.

4. 10. The method of claim 1, wherein the step of separating plastic and Teflon matrix from the particulate spent lithium ion secondary battery material is performed by air separation.

5. 2. The method of claim 1, wherein the lithium carbonate precipitate obtained in step (g) is further dried to obtain a dried lithium carbonate powder.

6. CH ４ , or C.H. ４ 2. The method according to claim 1, wherein the treatment of the separated particulate spent lithium ion secondary battery material in step (d) with air is carried out at a temperature of 100 to 900° C.

7. The CH ４ CH in a mixture of CH / air ４ The method of claim 1, wherein the partial pressure of is between 0.1% and 100% v / v.

8. 2. The method of claim 1, wherein the heating of the lithium carbonate filtrate at a temperature in step (g) is carried out at a temperature of 80 to 120° C.

9. 10. The method of claim 1, wherein the flux for smelting the other valuable metals comprises silica, carbon, calcium oxide, sodium oxide, alumina, iron oxide, or combinations thereof.

10. 2. The method of claim 1, wherein the step of treating the residue containing cobalt, other valuable metals, iron and non-metallic impurities with the flux of step (h) is carried out at a temperature of 1200-1500°C.

11. 2. The method of claim 1, wherein the valuable metal ingots of step (h) comprise ferrous or non-ferrous metals selected from cobalt, nickel, manganese, copper, aluminum, titanium, tin, lead, zinc, sodium, calcium, and combinations thereof.

Images