CN115747495A - Method for cleanly leaching ternary lithium battery waste - Google Patents
Method for cleanly leaching ternary lithium battery waste Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 49
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 48
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- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 4
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention provides a method for cleanly leaching ternary lithium battery waste, which comprises the steps of activating the ternary lithium battery waste by an oxygen-free roasting method, adding a citric acid solution to leach a positive electrode material in the waste after cooling, and filtering to obtain a leaching solution containing lithium, nickel, cobalt and manganese and leaching slag containing a negative electrode graphite material. Compared with the traditional oxidation roasting inorganic acid leaching ternary lithium battery waste, the leaching system is safer and more environment-friendly, can effectively retain graphite cathode materials, and reduces carbon emission. Has good engineering application value, economic value and environmental value. According to the invention, the structure of the anode material is destroyed and the high-valence metal oxide is reduced to the low-valence state, so that the anode material in the waste can be efficiently leached in the citric acid which is weak in acidity and is environment-friendly.
Description
Technical Field
The invention belongs to the technical field of regeneration of useful parts of waste storage batteries, and particularly relates to a method for cleanly leaching waste materials of a ternary lithium battery.
Background
The ternary lithium battery contains a large amount of lithium, nickel, cobalt, manganese, aluminum, copper and other metal elements and graphite, and the risk of polluting soil and water resources exists when the ternary lithium battery is randomly stacked or discarded. Along with the gradual popularization of new energy power automobiles in China, the retirement quantity of the power ternary lithium battery is also greatly increased. The ternary lithium battery waste contains a large amount of Li, ni, co, mn and other metal elements, and is a rare metal secondary resource with extremely high recovery value. However, the traditional recovery process has low recovery efficiency, and the waste acid and carbon emission in the recovery process are large, so that the process requirement of clean and efficient recovery under the background of 'double carbon' is difficult to meet. Therefore, the development of a core process for cleanly and efficiently separating and leaching valuable metal elements from ternary lithium battery wastes becomes a popular research topic in the technical field of metal resource recycling.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for cleanly leaching ternary lithium battery waste. Compared with the traditional method, the method can efficiently realize leaching of valuable metal elements in the ternary lithium battery waste, completely reserve the negative graphite material in the waste, and has an environment-friendly organic acid-citric acid leaching system. The method has good engineering application value, economic value and environmental value.
The invention provides a method for cleanly leaching ternary lithium battery waste, which comprises the steps of activating the ternary lithium battery waste by adopting an anaerobic roasting method, adding a citric acid solution to leach a positive electrode material in the waste after cooling, and filtering to obtain a leaching solution containing lithium, nickel, cobalt and manganese and leaching slag containing a negative electrode graphite material.
Preferably, the waste material of the ternary lithium battery is a mixture of a positive material and a negative material of the ternary lithium battery; and/or
The ternary lithium battery waste is powdery.
Preferably, the roasting is performed in a vacuum tube rotary furnace.
Preferably, the oxygen-free roasting is carried out under the protection of nitrogen or inert gas, and the roasting temperature is 490-500 ℃.
As a preferred scheme, the gas flow rate during the anaerobic roasting is 0.5L-3L/min; and/or
The roasting time is 2-3h.
Preferably, the cooling is natural cooling under the protection of nitrogen or inert gas, and the gas flow rate is 0.5L-3L/min.
Preferably, the liquid-solid ratio is 20mL/g when the citric acid solution is added.
Preferably, when the citric acid solution is added, the citric acid concentration is 2-3mol/L.
Preferably, when the citric acid solution is added for leaching, the leaching time is 2-3h.
Preferably, the filtration is suction filtration.
The invention has the following beneficial effects:
1. the roasting process of the invention is oxygen-free roasting, nitrogen or inert gas is introduced in the roasting process, and the leaching slag phase is basically graphite as can be seen from an EDS (electronic discharge spectroscopy) diagram. In addition, the graphite is roasted for 2 to 3 hours at the roasting temperature of 490 to 500 ℃, and under the condition, the graphite basically does not have violent reduction reaction with the metal oxide in the waste material, and if the roasting temperature is too high or the roasting time is too long, the reduction reaction is violent, and the graphite cathode material is consumed. In addition, the waste of the lithium battery is treated by an oxidizing roasting-acid leaching process in the industry at present, the oxidizing roasting burns away a graphite organic phase, the oxygen-free roasting of the invention well reserves negative graphite, carbon dioxide generated by roasting of the graphite and oxygen is avoided, and the graphite can be recycled. Therefore, compared with the traditional method for leaching the ternary lithium battery waste by oxidizing and roasting inorganic acid, the method has the advantages that a leaching system is safer and more environment-friendly, the graphite cathode material can be effectively reserved, and the carbon emission is reduced. Has good engineering application value, economic value and environmental value.
2. According to the invention, the structure of the anode material is destroyed and the high-valence metal oxide is reduced to the low-valence state, so that the anode material in the waste can be efficiently leached in the citric acid which is weak in acidity and is environment-friendly.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an XRD (X-ray diffraction) diagram and an SEM-EDS (scanning Electron microscope) -EDS diagram of leached slag phase of the calcined ternary lithium battery waste in example 1.
FIG. 2 is an XRD (X-ray diffraction) diagram and an SEM-EDS (scanning Electron microscope-EDS) diagram of a leached slag phase of the calcined ternary lithium battery waste material in comparative example 1.
FIG. 3 is an XRD (X-ray diffraction) diagram and an SEM-EDS (scanning Electron microscope-EDS) diagram of a leached slag phase of the calcined ternary lithium battery waste material in comparative example 2.
FIG. 4 is an XRD (X-ray diffraction) pattern of the calcined ternary lithium battery waste and an SEM-EDS (scanning Electron microscope) -EDS pattern of a leached slag phase of the calcined ternary lithium battery waste in comparative example 3.
FIG. 5 is an XRD pattern of the calcined ternary lithium battery waste and an SEM-EDS pattern of a leached slag phase in comparative example 4.
Detailed Description
The following examples are intended to facilitate a better understanding of the invention, but are not intended to limit the invention thereto. The experimental procedures in the following examples are conventional unless otherwise specified.
The principle of the method of the invention is as follows: activating the ternary lithium battery powder waste by adopting an oxygen-free roasting method, destroying the structure of the positive electrode material and reducing the high-valence metal oxide into a low-valence state, so that the positive electrode material in the waste can be efficiently leached in the citric acid which is weak in acid and environment-friendly, lithium, nickel, cobalt and manganese elements are in a leaching solution, and the negative electrode graphite material is retained in a leaching slag phase.
The method for cleanly leaching the ternary lithium battery waste comprises the following steps:
activating the ternary lithium battery waste by adopting an oxygen-free roasting method, cooling, adding a citric acid solution to leach the positive electrode material in the waste, and filtering to obtain a leaching solution containing lithium, nickel, cobalt and manganese and a leaching residue containing a negative electrode graphite material.
According to some embodiments of the present application, the waste material of the ternary lithium battery is a mixture of a positive electrode material and a negative electrode material of the ternary lithium battery.
According to some embodiments of the present application, the ternary lithium battery waste is in powder form.
According to some embodiments of the present application, the oxygen-free firing is performed under nitrogen or inert gas shielding at a firing temperature of 490 to 500 ℃.
In some embodiments, the oxygen-free calcination has a gas flow rate of 0.5L to 3L/min.
When the gas flow rate is less than 0.5L/min, air enters the tube furnace, the graphite consumption is large, and when the gas flow rate is more than 3L/min, the gas flow rate is too high, and the waste of the powder can be blown.
In some embodiments, the firing time is 2 to 3 hours.
If the roasting time is less than 2 hours, the structural damage degree of the anode material is insufficient, the high-valence metal oxide is difficult to leach, and if the roasting time is more than 3 hours, a large amount of valuable metal elements in the waste are reduced into metal simple substances, and leaching in citric acid is not suitable, so that the leaching efficiency is reduced.
According to some embodiments of the present application, the firing is performed in a vacuum tube rotary furnace.
During roasting, the rotating speed of the rotary furnace can be 30-60rpm, the rotating limit of the equipment is 60rpm, and the rotating speed is suitable for improving the heat transfer efficiency in the powder heating process.
According to some embodiments of the present application, the cooling is natural cooling under the protection of nitrogen or inert gas, so that the high-temperature metal oxide is prevented from contacting with air to form a refractory high-valence oxide again, and the gas flow rate is 0.5L-3L/min.
When the gas flow rate is less than 0.5L/min, air enters the tube furnace, the graphite consumption is large, and when the gas flow rate is more than 3L/min, the gas flow rate is too high, so that waste of powder can be blown.
According to some embodiments of the present application, the liquid-to-solid ratio is 20mL/g when the citric acid solution is added.
The liquid-solid ratio is calculated according to the content of metal elements in the waste, the acid content is generally 50% more than that of the acid which just reacts to ensure the leaching efficiency, the leaching efficiency is reduced when the solid content is too high, and the acid waste is caused when the solid content is too low.
According to some embodiments of the present application, the citric acid solution is added to a citric acid concentration of 2 to 3mol/L.
Citric acid is an acid with stronger acidity in organic acids, if other acids such as acetic acid or malic acid are used, the leaching efficiency is low, and the citric acid is easier to treat in subsequent waste liquid than inorganic acids (sulfuric acid and hydrochloric acid) and can be decomposed by heating. Too high a citric acid concentration will cause waste and a citric acid concentration below the lower limit will cause a low leaching efficiency.
According to some embodiments of the present application, the leaching time is 2-3h when adding citric acid solution for leaching.
The leaching time is less than 2 hours, so that the leaching rate of the target metal element is reduced, the leaching time is more than 3 hours, the leaching rate is basically unchanged, and the energy consumption is increased.
According to some embodiments of the present application, the leaching is performed in an acid-resistant stirred leaching tank.
According to some embodiments of the application, the filtration is suction filtration.
By applying the method, the leaching rates of lithium, nickel, cobalt and manganese elements are all higher than 95%; the pure negative graphite material is retained.
Example 1
The method for cleanly leaching the ternary lithium battery waste comprises the following steps:
selecting ternary lithium battery waste (mixed powder of a positive electrode and a negative electrode), weighing a certain amount of waste, placing the waste in a vacuum tube type rotary furnace, regulating the roasting temperature to 500 ℃ under the nitrogen atmosphere at the nitrogen flow rate of 3L/min, and roasting the powdery ternary lithium battery waste for 3 hours; and naturally cooling the roasted ternary lithium battery waste in a nitrogen atmosphere, wherein the nitrogen flow rate is 3L/min. And cooling, placing in an acid-resistant stirring leaching kettle, and adding a leaching agent citric acid solution, wherein the liquid-solid ratio is 20mL/g, and the concentration of the citric acid solution is 3mol/L. Leaching for 2h, and then carrying out suction filtration to obtain leaching solution of lithium, nickel, cobalt and manganese and leaching residue of the negative graphite material. The leaching rates of lithium, nickel, cobalt and manganese are respectively calculated to be 98.11%, 95.23%, 95.35% and 97.97% by detecting the leaching solution by an ICP method. XRD detection of the roasted ternary lithium battery waste and SEM-EDS detection of a leached slag phase are shown in figure 1.
FIG. 1 is an XRD (X-ray diffraction) pattern of calcined ternary lithium battery waste and an SEM-EDS (scanning Electron microscope) -EDS (scanning Electron Spectroscopy) pattern of leached slag phase in example 1.
Comparative example 1
The method for leaching the ternary lithium battery waste material comprises the following steps:
selecting ternary lithium battery waste (mixed powder of a positive electrode and a negative electrode), weighing a certain amount of waste, placing the waste in a vacuum tube type rotary furnace, roasting the powdery ternary lithium battery waste for 3 hours at the roasting temperature of 400 ℃ under the nitrogen atmosphere at the nitrogen flow rate of 3L/min; and naturally cooling the roasted ternary lithium battery waste in a nitrogen atmosphere, wherein the nitrogen flow rate is 3L/min. After cooling, placing the mixture into an acid-resistant stirring leaching kettle, and adding a leaching agent citric acid, wherein the liquid-solid ratio is 20mL/g, and the concentration of the citric acid is 3mol/L. Leaching for 2h, and then carrying out suction filtration to obtain leaching solutions of lithium, nickel, cobalt and manganese and leaching residues of the negative graphite material. The leaching rates of lithium, nickel, cobalt and manganese are respectively 94.57%, 90.98%, 91.20% and 93.56% by ICP method detection. XRD detection of the roasted ternary lithium battery waste and SEM-EDS detection of the leached slag phase are shown in figure 2.
FIG. 2 is an XRD (X-ray diffraction) pattern of the calcined ternary lithium battery waste and an SEM-EDS (scanning Electron microscope) -EDS (scanning Electron Spectroscopy) pattern of a leached slag phase of the calcined ternary lithium battery waste in comparative example 1.
Comparative example 2
The method for leaching the ternary lithium battery waste material comprises the following steps:
selecting ternary lithium battery waste (mixed powder of a positive electrode and a negative electrode), weighing a certain amount of waste, placing the waste in a vacuum tube type rotary furnace, roasting the powdery ternary lithium battery waste for 3 hours at the roasting temperature of 600 ℃ under the nitrogen atmosphere at the nitrogen flow rate of 3L/min; and naturally cooling the roasted ternary lithium battery waste in a nitrogen atmosphere at the nitrogen flow rate of 3L/min. After cooling, placing the mixture into an acid-resistant stirring leaching kettle, and adding a leaching agent citric acid, wherein the liquid-solid ratio is 20mL/g, and the concentration of the citric acid is 3mol/L. Leaching for 2h, and then carrying out suction filtration to obtain leaching solution of lithium, nickel, cobalt and manganese and leaching residue of the negative graphite material. The leaching rates of lithium, nickel, cobalt and manganese are respectively calculated to be 98.30%, 95.18%, 88.10.35% and 97.10% by detecting the leaching solution by an ICP method. The XRD detection of the roasted ternary lithium battery waste and the SEM-EDS detection of the leached slag phase are shown in figure 3.
FIG. 3 is an XRD (X-ray diffraction) pattern of the calcined ternary lithium battery waste and an SEM-EDS (scanning Electron microscope) -EDS (scanning Electron Spectroscopy) pattern of a leached slag phase of the calcined ternary lithium battery waste in comparative example 2.
As can be seen from fig. 1 to 3, the method of the present invention can destroy the structure of the positive electrode material and reduce the high valence metal oxide to the low valence metal oxide, so that the positive electrode material in the waste can be efficiently leached in the citric acid which is weak in acidity and is environmentally friendly.
Example 1 after roasting, valence states of valuable metal elements in the ternary lithium battery waste are reduced (nickel, cobalt and manganese are +2 valence, and lithium is +1 valence), the structure of the positive electrode material is seriously damaged, and the leaching effect in a citric acid leaching agent is excellent. The roasted product obtained in comparative example 1 has a higher valence state, the structural damage of the positive electrode material is relatively less serious than that of example 1, and the leaching rate of the valuable metal of comparative example 1 is lower.
The cobalt element in the baked product positive electrode material in comparative example 2 was reduced to the simple substance, and the leaching rate of cobalt was lower than that in comparative example 1 because the reaction rate of the simple substance of cobalt with citric acid was lower than that of cobalt oxide with citric acid.
According to the experimental result, the oxygen-free roasting before citric acid leaching is carried out on the ternary lithium battery waste by applying the method, the valence state of the valuable metal element in the roasted ternary lithium battery waste is reduced, the structure of the anode material is damaged, and the reaction of low-valence oxide in the waste and citric acid is promoted.
The method can effectively destroy the structure of the anode material and reduce the high-valence metal oxide into the low-valence metal oxide, so that the anode material in the waste can be efficiently leached in the citric acid which is weak in acidity and environment-friendly, and simultaneously, the graphite cathode material can be effectively reserved, and the carbon emission is reduced. Therefore, the invention has better engineering application value, economic value and environmental value.
Example 2
The method for cleanly leaching the ternary lithium battery waste comprises the following steps:
selecting ternary lithium battery waste (mixed powder of a positive electrode and a negative electrode), weighing a certain amount of waste, placing the waste in a vacuum tube type rotary furnace, regulating the roasting temperature to 490 ℃ under the nitrogen atmosphere at the nitrogen flow rate of 0.5L/min, and roasting the powdery ternary lithium battery waste for 2 hours; and naturally cooling the roasted ternary lithium battery waste under the nitrogen atmosphere, wherein the nitrogen flow rate is 0.5/min. After cooling, placing the mixture into an acid-resistant stirring leaching kettle, and adding a leaching agent citric acid solution, wherein the liquid-solid ratio is 20mL/g, and the concentration of the citric acid solution is 2mol/L. Leaching for 2h, and then carrying out suction filtration to obtain leaching solutions of lithium, nickel, cobalt and manganese and leaching residues of the negative graphite material.
The detection method was the same as in example 1. The detection result is as follows: the leaching rates of lithium, nickel, cobalt and manganese are respectively 98.12%, 95.21%, 95.28% and 97.54%.
Example 3
The method for cleanly leaching the ternary lithium battery waste comprises the following steps:
selecting ternary lithium battery waste (mixed powder of a positive electrode and a negative electrode), weighing a certain amount of waste, placing the waste in a vacuum tube type rotary furnace, roasting the powdery ternary lithium battery waste for 2.5 hours at the roasting temperature of 495 ℃ under the nitrogen atmosphere at the nitrogen flow rate of 2L/min; and naturally cooling the roasted ternary lithium battery waste under the nitrogen atmosphere, wherein the nitrogen flow rate is 2L/min. After cooling, the mixture is placed in an acid-resistant stirring leaching kettle, and a leaching agent citric acid solution is added, wherein the liquid-solid ratio is 20mL/g, and the concentration of the citric acid solution is 2.5mol/L. Leaching for 2h, and then carrying out suction filtration to obtain leaching solutions of lithium, nickel, cobalt and manganese and leaching residues of the negative graphite material.
The detection method was the same as in example 1. The detection result is as follows: the leaching rates of lithium, nickel, cobalt and manganese are respectively 98.01 percent, 95.22 percent, 95.14 percent and 97.36 percent.
As can be seen from examples 1 to 3, the leaching rates of lithium, nickel, cobalt and manganese were all high when the calcination temperature was between 490 and 500 ℃.
Comparative example 3
The method for leaching the ternary lithium battery waste comprises the following steps:
selecting ternary lithium battery waste (mixed powder of a positive electrode and a negative electrode), weighing a certain amount of waste, placing the waste in a vacuum tubular rotary furnace, roasting the powdery ternary lithium battery waste for 3 hours at the roasting temperature of 500 ℃ under the nitrogen atmosphere at the nitrogen flow rate of 3L/min; and naturally cooling the roasted ternary lithium battery waste in a nitrogen atmosphere at the nitrogen flow rate of 3L/min. And cooling, placing in an acid-resistant stirring leaching kettle, and adding a leaching agent malic acid solution, wherein the liquid-solid ratio is 20mL/g, and the concentration of the malic acid solution is 3mol/L. Leaching for 2h, and then carrying out suction filtration to obtain leaching solution of lithium, nickel, cobalt and manganese and leaching residue of the negative graphite material. The leaching rates of lithium, nickel, cobalt and manganese are calculated to be 93.11%, 92.23%, 84.35% and 93.97% respectively by detecting the leaching solution by an ICP method. XRD detection and leached slag phase SEM-EDS detection of the roasted ternary lithium battery waste leachate are shown in figure 4.
FIG. 4 is an XRD (X-ray diffraction) diagram and an SEM-EDS (scanning Electron microscope-EDS) diagram of a leached slag phase of the calcined ternary lithium battery waste material in comparative example 3.
Comparative example 4
The method for leaching the ternary lithium battery waste material comprises the following steps:
selecting ternary lithium battery waste (mixed powder of a positive electrode and a negative electrode), weighing a certain amount of waste, placing the waste in a vacuum tube type rotary furnace, regulating the roasting temperature to 500 ℃ under the nitrogen atmosphere at the nitrogen flow rate of 3L/min, and roasting the powdery ternary lithium battery waste for 3 hours; and naturally cooling the roasted ternary lithium battery waste in a nitrogen atmosphere, wherein the nitrogen flow rate is 3L/min. After cooling, placing the mixture in an acid-resistant stirring leaching kettle, and adding a leaching agent acetic acid solution, wherein the liquid-solid ratio is 20mL/g, and the concentration of the acetic acid solution is 3mol/L. Leaching for 2h, and then carrying out suction filtration to obtain leaching solutions of lithium, nickel, cobalt and manganese and leaching residues of the negative graphite material. The leaching rates of lithium, nickel, cobalt and manganese are respectively 83.11%, 75.23%, 64.35% and 79.97% by calculation through ICP method detection leaching solution. XRD detection of the roasted ternary lithium battery waste leachate and SEM-EDS detection of a leached slag phase are shown in figure 5.
FIG. 5 is an XRD (X-ray diffraction) diagram and an SEM-EDS (scanning Electron microscope-scattering system) diagram of leached slag phase of the calcined ternary lithium battery waste material in comparative example 4.
XRD (X ray diffraction) of figures 1, 4 and 5 are the same figures, and are phase diagrams of ternary lithium battery waste after oxygen-free roasting at 500 ℃, wherein in the phase diagrams, the phase diagrams are extracted by citric acid in example 1, and are extracted by malic acid and acetic acid in comparative example 3 and 4 respectively.
Comparing example 1 with comparative examples 3 and 4, it can be seen that the leaching rates of lithium, nickel, cobalt, and manganese and the change in slag phase are large in the case of changing the leaching agent alone.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for cleanly leaching ternary lithium battery waste is characterized by comprising the following steps: activating the ternary lithium battery waste by adopting an anaerobic roasting method, adding a citric acid solution to leach the positive electrode material in the waste after cooling, and filtering to obtain leachate containing lithium, nickel, cobalt and manganese and leached slag containing a negative electrode graphite material.
2. The method for clean leaching of ternary lithium battery waste as claimed in claim 1, characterized in that: the waste material of the ternary lithium battery is a mixture of a positive material and a negative material of the ternary lithium battery; and/or
The ternary lithium battery waste is powdery.
3. The method for clean leaching of ternary lithium battery waste as claimed in claim 1, characterized in that: the roasting is carried out in a vacuum tube type rotary furnace.
4. The method for clean leaching of ternary lithium battery waste as claimed in claim 1, wherein: the oxygen-free roasting is carried out under the protection of nitrogen or inert gas, and the roasting temperature is 490-500 ℃.
5. The method for clean leaching of ternary lithium battery waste as claimed in claim 1, characterized in that: the gas flow rate during the anaerobic roasting is 0.5L-3L/min; and/or
The roasting time is 2-3h.
6. The method for clean leaching of ternary lithium battery waste as claimed in claim 1, characterized in that: the cooling is natural cooling under the protection of nitrogen or inert gas, and the gas flow rate is 0.5L-3L/min.
7. The method for clean leaching of ternary lithium battery waste as claimed in claim 1, characterized in that: when the citric acid solution is added, the liquid-solid ratio is 20mL/g.
8. The method for clean leaching of ternary lithium battery waste as claimed in claim 1, wherein: when the citric acid solution is added, the concentration of the citric acid is 2-3mol/L.
9. The method for clean leaching of ternary lithium battery waste as claimed in claim 1, characterized in that: when citric acid solution is added for leaching, the leaching time is 2-3h.
10. The method for clean leaching of ternary lithium battery waste as claimed in claim 1, characterized in that: the filtration is suction filtration.
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