CN112047335B - Combined treatment method for black powder of waste lithium ion battery - Google Patents
Combined treatment method for black powder of waste lithium ion battery Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of waste electrode material recovery, and particularly discloses a combined treatment method of waste lithium ion battery black powder, which comprises the steps of putting the waste lithium ion battery black powder into strong oxidizing acid liquid for oxidation treatment, and then carrying out solid-liquid separation to obtain oxidized powder; granulating the oxidized powder; obtaining secondary particles; heating the secondary particles to 600-1200 ℃ at a heating rate of 20-50 ℃/min, and roasting at a heat preservation pressure of 10-500 Pa; soaking the roasted material in water and then performing acid leaching treatment; mixing the obtained leaching solution with the oxidation treatment solution in the step (1), and recovering a positive electrode material; the leached residue after acid leaching is the recycled graphite. The technical scheme of the invention can realize the combined treatment of the anode and the cathode, and not only can obtain the graphite material with high electrochemical activity, particularly high quick charge stability, but also can obtain the anode material by recycling with high recovery rate.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery recovery, and particularly relates to a combined treatment method of waste lithium ion battery black powder.
Background
The rapid increase of the usage amount of 3C electronic products and the gradual industrialization and scale of new energy automobiles lead the rejection amount of the lithium ion battery as a key component to generate well-jet explosion in recent years, and the contradiction between the development of battery energy storage devices and the environment and resources is gradually highlighted. The lithium ion battery can not be effectively recycled, and has extremely high environmental protection, economic benefit and social value.
The lithium ion battery is mainly composed of a positive electrode, a negative electrode, a diaphragm, electrolyte and a shell. Currently, the main work of recycling lithium ion batteries is focused on the enrichment and recovery of valuable metals such as lithium, cobalt, nickel, manganese and the like contained in the positive electrode. The negative electrode material of the lithium ion battery is still graphite currently, and the negative electrode material is mainly divided into natural graphite and artificial graphite. The natural graphite has limited reserves, and needs to be spheroidized or surface-coated to improve the use efficiency, and high-temperature treatment is often needed in the process. In the treatment of waste lithium ion batteries, the negative graphite is usually treated by a pyrogenic process or directly dumped. This not only aggravates the environmental pollution, but also causes waste of resources. The recovery of the high-purity graphite material through a simple process flow is a key technical problem to be solved in the aspect of current negative electrode recovery.
The waste lithium ion battery black powder is a mixture consisting of anode powder and cathode powder of the waste lithium ion battery, and contains organic matters, electrolyte salt, nickel, cobalt, manganese, copper, aluminum, carbonaceous materials and the like. Among them, the carbonaceous material is mainly graphite (containing artificial graphite having a carbon-coated surface), a conductive agent, and the like, which are negative electrode active materials. Therefore, it is necessary to remove impurities from the material composition in order to improve the purity of the graphite material. In addition, the microstructure of the retired lithium ion battery graphite negative electrode material is damaged after long-term charge and discharge, and the structural defects in the microstructure can cause the lithium ion battery graphite negative electrode material to contain an undetachable lithium source and be difficult to directly recycle. Although the conventional acid washing process can purify the lithium-doped lithium iron phosphate, the lithium-doped lithium iron phosphate still has poor lithium intercalation and deintercalation properties because the microstructure is not repaired, and particularly, the first irreversible capacity loss caused by structural defects is large. Patent CN107887666B discloses a process for mixing, stripping, leaching and graphitizing a waste lithium ion battery negative electrode sheet and a separating agent to recover graphite, wherein the process adopts graphitization to repair the microstructure of waste carbon slag, so that the graphite lattice is more regular, but the graphitization process has high energy consumption, and the cost is not reasonable when the waste lithium ion battery negative electrode material of which the raw material is artificial graphite is graphitized again.
Disclosure of Invention
The invention provides a combined treatment method for waste lithium ion battery black powder, which aims to solve the problems that the waste lithium ion black powder is difficult to be synchronously and effectively treated, the recovery purity of a negative electrode material is low, the recovery process is complex, the performance of the recovered negative electrode material is not repaired and the like.
The second purpose of the invention is to provide an application method of the graphite material recovered by the combined treatment method, aiming at improving the electrochemical performance of the recovered negative electrode material, changing waste into valuable and improving the commercial application value of the negative electrode material.
A combined treatment method of black powder of waste lithium ion batteries comprises the following steps:
step 1:
putting the waste lithium ion battery black powder into strong oxidizing acid liquor for oxidation treatment, and then carrying out solid-liquid separation to obtain oxidation treatment powder and oxidation treatment liquid;
step 2:
granulating the oxidized powder; obtaining secondary particles;
and step 3:
heating the secondary particles to 600-1200 ℃ at a heating rate of 20-50 ℃/min, and roasting at a heat preservation pressure of 10-500 Pa;
and 4, step 4:
soaking the roasted material in water and then performing acid leaching treatment; leaching residues of acid leaching are recovered graphite;
the obtained leachate (leachate obtained by water leaching and acid leaching) is mixed with the oxidation treatment solution of step 1, and the positive electrode material is recovered.
In the prior art, methods for respectively treating the positive electrode and the negative electrode of more retired electrode materials are reported, and methods for jointly treating the positive electrode and the negative electrode are less reported, which mainly aims to realize the recovery of the electrochemical performance of the waste graphite on the premise that the mutual interference problem of the joint treatment of the positive electrode and the negative electrode is difficult to effectively solve and the recycling of the positive electrode material is difficult to effectively realize in the prior art. Aiming at the technical problems of high recovery difficulty of the positive electrode material and unsatisfactory electrochemical performance of the recovered graphite in the combined treatment of the positive electrode material and the negative electrode material, the invention innovatively provides the combined treatment method, which is used for oxidizing black powder, performing phase oxidation recovery on the positive electrode material and performing oxidation intercalation on the graphite to realize proper amount of oxygen hybridization and metal modification of the graphite material; the spacing between graphite layers is increased, and further the efficient leaching of metal elements doped between the graphite layers is realized; on the basis of the oxidation treatment of the positive and negative electrodes, the subsequent granulation treatment and the sintering treatment under the special pressure under the rapid temperature rise are further matched, so that the graphite structure can be repaired, the graphitization degree and the purity of the material can be improved, the performance of the graphite can be effectively repaired, the performance of the graphite can be unexpectedly superior to that of a new graphite material, and the quick charging stability of the recycled material can be improved. The technical scheme of the invention not only can effectively improve the electrochemical performance of the recycled graphite, but also is beneficial to the effective separation of the anode material and the cathode material, and is beneficial to the efficient recycling of the anode material.
The black powder is a mixture of anode powder and cathode powder of the waste lithium ion battery. The water content is 10-35%.
The black powder is a material obtained by stripping the current collector from the positive electrode and the negative electrode, and the stripping means of the current collector can be the existing ones, such as manual stripping, aqueous solution stripping (mainly the negative electrode) or organic solvent stripping (mainly the positive electrode).
The lithium ion battery anode powder is one or a mixture of more of lithium ferrite, lithium manganate, ternary lithium cobalt phosphate and the like.
The negative electrode powder of the lithium ion battery is graphite-based natural or artificial graphite negative electrode powder.
The research of the invention finds that the combined process of oxidation, granulation, rapid heating and sintering under special pressure is adopted for the black powder containing the anode material and the cathode material, so that the synergy of the anode and cathode treatment can be realized, the structure reconstruction and hybridization of the cathode material can be unexpectedly facilitated, the graphite material with excellent electrochemical performance, particularly excellent rapid charging performance can be obtained, and in addition, the high-recovery obtaining of the anode material is facilitated. The technical scheme of the invention can realize good separation of the anode and the cathode based on the combination of the processes and the cooperation of the processing objects, and is beneficial to realizing the recovery of the cathode with high electrochemical performance.
The research of the invention finds that under the combined system of the black powder, in order to improve the electrochemical performance, particularly the quick charging performance, of the recovered graphite, the degree of oxidation intercalation and the hybridization degree of oxygen and metal need to be controlled, so that the electrochemical performance of the recovered graphite can be improved unexpectedly.
Preferably, the strong oxidizing acid solution is at least one of concentrated sulfuric acid, concentrated nitric acid, and perchloric acid.
Preferably, the liquid-solid ratio of the strong oxidizing acid liquid to the waste lithium ion battery black powder is 3-10 mL/g. That is, 3-10 mL of a strong oxidizing acid solution is used per 1g of the black powder.
Preferably, the oxidation temperature is 0-60 ℃, preferably 0-30 ℃, and the oxidation time is preferably 0.5-4 h, preferably 2-4 h.
The research of the invention finds that under the condition of controlling the type, the oxidation temperature and the oxidation time of the strong oxidizing acid liquid, the method is beneficial to improving the electrochemical performance of the recovered graphite under the condition of matching with the subsequent granulation and sintering processes, and is particularly beneficial to improving the quick charging performance of the recovered graphite.
The method innovatively and previously carries out oxidation treatment on the black powder, so that the method is beneficial to oxidation intercalation, oxygen hybridization and metal hybridization of graphite, is also beneficial to pre-recovering part of positive active materials, and is also beneficial to pre-separating positive and negative materials on the premise of realizing intercalation and modification of a negative electrode.
In the invention, the powder material after oxidation treatment is granulated; secondary particles were obtained. It has been found that in the process of the present invention, the electrochemical properties of the recovered graphite can be unexpectedly improved by performing the granulation process.
Preferably, the granulation is a structure of secondary granules prepared by using commercial granulation equipment, and the D50 of the obtained secondary granules is 18-100 μm; preferably 50 to 100 μm.
In the invention, based on the oxidation and granulation processes, a sintering process is further matched, and particularly based on the combined control of the heating rate, the pressure and the temperature in the sintering process, the electrochemical performance of graphite can be unexpectedly utilized, and the recovery of a positive electrode material is facilitated.
In the invention, the heating rate needs to be controlled within the required range of 20-50 ℃/min, and the quick charging stability of the recycled graphite material is greatly influenced if the heating rate is not controlled within the range.
Preferably, the temperature rise rate is 30-50 ℃/min.
In the invention, the temperature can be raised to the required temperature at the temperature raising rate under normal pressure, and then the pressure of the system is controlled under the required condition, and the heat-preservation sintering treatment is carried out. The present inventors have found that controlling the sintering at the stated pressures helps to unexpectedly improve the flash-fill stability of the recovered graphite.
Preferably, the pressure in the heat-preservation sintering process is 10-200 Pa.
Preferably, the temperature of the heat-preservation sintering process is 800-1200 ℃.
Preferably, the sintering time is 2-8 h, the heat preservation process is finished, and natural cooling is carried out.
Preferably, the atmosphere in the sintering process is a non-oxygen atmosphere, and preferably one or more protective atmospheres such as nitrogen, argon, hydrogen, helium and the like.
In the invention, the sintered material is leached by a wet method, so that the electrochemical performance of the recovered graphite is further improved, and the recovery performance of the anode is further improved.
The wet leaching comprises water leaching and acid leaching which are sequentially carried out; for example, the roasted material is subjected to water leaching treatment to obtain a water leaching solution and water leaching slag, the water leaching slag is placed in an acid solution for acid leaching treatment, and solid-liquid separation is carried out to obtain an acid leaching solution and acid leaching slag; the acid leaching residue is the recycled graphite.
The acid liquor adopted in the acid leaching process is at least one of hydrochloric acid, sulfuric acid and nitric acid; the concentration is 2-6M. Preferably, the acid solution may be the solution after oxidation treatment in step 1.
In the invention, under the acid leaching in the step 4, metal replacement can be carried out between graphite layers and on the surface of the graphite layers, so that the efficient recovery of the positive electrode material is facilitated on the premise of improving the electrochemical performance of the graphite. Research shows that the comprehensive recovery rate of the valuable metals of the positive electrode can be higher than 99.5 percent by mixing and recovering the oxidation treatment solution in the step 1 and the leaching solution (comprising a water leaching solution and an acid leaching solution).
In the invention, the leaching residue (acid leaching residue) in the liquid phase leaching process is collected, and the recovered graphite is obtained through conventional treatments such as drying, screening, shaping, demagnetizing, packaging and the like.
The combined treatment method provided by the invention prepares the graphite material with the quick charging performance by using the waste lithium ion battery black powder, and the graphite material has high graphitization degree and high purity and has a graphite layer spacing larger than that of a standard graphite material. The graphitization degree of the composite material is 92-99.6%, and the ash content of the composite material is less than 0.02%.
The invention also provides application of the graphite recovered by the method as a negative electrode active material of a lithium ion battery.
The invention also discloses a lithium ion battery, and the negative active material is graphite recovered by the method.
Researches show that based on the recovery method, a new graphite recovery material with excellent electrochemical performance can be obtained, and the resource utilization of waste materials is realized.
The principle and advantages of the invention are as follows:
(1) the black powder containing the positive electrode and the negative electrode is subjected to oxidation treatment innovatively, the leaching of the positive electrode is realized, the graphite oxidation intercalation and oxidation and metal hybridization of the negative electrode are synchronously realized, and the electrochemical performance, particularly the quick charging performance of the recovered graphite can be unexpectedly improved by further matching granulation with sintering treatment under the heating rate, pressure and temperature.
(2) On the basis of carrying out the oxidation-granulation and the sintering treatment under the conditions on the black powder, the combined control of the oxidation process and the sintering process conditions is further matched, which is beneficial to further improving the electrochemical performance of the graphite; moreover, the graphite is subjected to layer expanding treatment in the oxidation process, so that not only can partial metal be leached in the process, but also the metal included between graphite layers is further leached in the subsequent acid leaching process of the graphite after layer expanding, so that the efficient recovery of the positive electrode material is facilitated, the comprehensive recovery rate of the positive electrode valuable metal is higher than 99.5%, and the high-performance and high-purity graphite material is obtained.
Therefore, the implementation of the method can effectively realize the separation of the graphite powder and the valuable metal liquid, and can obtain the graphite powder with high purity, high graphitization degree, large interlayer spacing and quick charging property.
The patented method has the advantages of short production flow, simple process, controllable process and the like, and can be used for large-scale production by utilizing the existing mature industry.
Drawings
FIG. 1 is an SEM image of the black powder raw material used in example 1, and the irregular morphology of the mixed material can be seen.
Fig. 2 is an XRD chart of the black powder raw material used in example 1, and it can be seen that the material contains the ternary positive electrode and graphite negative electrode components.
Figure 3 is an XRD pattern of the graphite product obtained in example 1. The material can be seen to have a curved graphite characteristic peak, and the peak is high and sharp, which shows that the material has a very regular graphitized structure, and has high graphitization degree and high purity.
Fig. 4 is an SEM image of the graphite product obtained in example 1. The resulting graphite material was seen to be particulate and to have a flake structure, indicating that the graphite was partially exfoliated.
Fig. 5 is an XRD pattern of the graphite product obtained in comparative example 1. It can be seen that the graphite has a graphite characteristic peak, but the graphite contains an impurity characteristic peak, which is caused by the poor purity effect of the graphite in the leaching process.
Fig. 6 is an SEM image of the graphite product obtained in comparative example 1. The particle surface was seen to have no apparent lamellar structure, indicating that it was not exfoliated.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to the following examples.
The graphitization degree of the materials in the embodiments and the comparative examples of the invention is determined by XRD, the purity is characterized by ash content test, and the first coulomb efficiency, the first reversible capacity, the capacity retention rate and the high-rate charge-discharge performance of the materials are determined by assembling smears and button cells of the obtained materials.
The comprehensive recovery rate of the valuable metals of the positive electrode is determined by measuring the content of the valuable metals in the black powder before treatment and the content of the metals in the pickle liquor through ICP.
Example 1:
putting 100g of waste lithium ion battery black powder (the positive pole is NCM (percent of carbon) 8:1:1, and the negative pole is graphite) into 500ml of concentrated sulfuric acid, stirring and reacting for 2 hours at 0 ℃, and carrying out solid-liquid separation; the obtained filtrate (oxidation leaching liquid) is reserved for standby;
uniformly mixing the obtained powder materials in a mixer, and placing the mixture in a granulator for secondary granulation, wherein the material D50 is controlled to be 50 microns;
thirdly, placing the obtained material in a tubular furnace under the nitrogen atmosphere, raising the temperature to 1000 ℃ at the normal pressure at the heating rate of 30 ℃/min, then carrying out vacuum-pumping treatment on the system to ensure that the pressure of the system is 100Pa, and naturally cooling after heat preservation for 4 hours;
fourthly, mixing the obtained materials according to a liquid-solid ratio of 5: 1, dispersing in deionized water for slurrying, performing suction filtration after stirring reaction for 4 hours, and placing filter residues in a liquid-solid ratio of 3: 1, adding 2M sulfuric acid solution into the filtrate obtained in the step I, uniformly mixing, stirring for reacting for 4 hours, performing suction filtration and washing, and measuring the content of valuable metals in the obtained filtrate; the obtained solid is graphite leaching residue;
fifthly, drying, crushing, screening, shaping, demagnetizing and packaging the leached residues.
The black powder raw material adopted in this embodiment is powder obtained by manually detaching the battery and then manually peeling the anode powder of the positive and negative electrode sheets. As can be seen from the attached figure 2, the main crystal components are as follows: a ternary positive electrode and a graphite negative electrode. After treatment, the graphitization degree of the obtained material is 98%, the ash content is 0.01%, the reversible specific capacity under 0.2C is 362mAh/g, the reversible specific capacity under 2C is 302mAh/g, and the reversible specific capacity under 5C is 264 mAh/g. The comprehensive leaching rate of the valuable metals on the positive electrode is 99.8 percent.
Commercial graphite materials were used for the tests under the same conditions. The graphitization degree of the material is 99%, the ash content is 0.002%, the reversible specific capacity under 0.2C is 357mAh/g, the reversible specific capacity under 2C is 197mAh/g, and the reversible specific capacity under 5C is 79 mAh/g. Therefore, the graphite material recovered by the method has better rapid charging stability.
The waste lithium batteries (same as example 1) were disassembled by hand to obtain graphite powder separately, which was tested under the same conditions. The result shows that the graphitization degree is 82%, the ash content is 5.9%, the reversible specific capacity under 0.2C is 261mAh/g, the reversible specific capacity under 2C is 82mAh/g, and the reversible specific capacity under 5C is 21 mAh/g. Therefore, the specific capacity of the retired graphite (the graphite before being treated in the case) is low, and the fast charging stability is poor.
Example 2:
putting 100g of waste lithium ion battery black powder (same as example 1) into 400ml of concentrated nitric acid, stirring and reacting for 4 hours at the temperature of 20 ℃, and carrying out solid-liquid separation; the obtained filtrate is reserved for standby;
uniformly mixing the obtained powder materials in a mixer, and placing the mixture in a granulator for secondary granulation, wherein the material D50 is controlled to be 60 mu m;
thirdly, placing the obtained material in a tubular furnace under the argon atmosphere, raising the temperature to 800 ℃ at the normal pressure at the heating rate of 50 ℃/min, vacuumizing the system to enable the pressure of the system to be 50Pa, preserving the heat for 4 hours, and naturally cooling;
fourthly, mixing the roasted material with a liquid-solid ratio of 5: 1, dispersing in deionized water for slurrying, performing suction filtration after stirring reaction for 4 hours, and placing filter residues in a liquid-solid ratio of 3: slurrying in 2M sulfuric acid solution of 1, stirring for reaction for 4 hours, carrying out suction filtration and washing, and combining the filtrate with the filtrate in the step I for measuring the metal content;
fifthly, drying, crushing, screening, shaping, demagnetizing and packaging the leached residues.
The black powder raw material adopted in this embodiment is a powder obtained by pretreating the positive and negative electrode sheets with water and NMP. After the experimental treatment, the graphitization degree of the obtained material is 97%, the ash content is 0.008%, the reversible specific capacity under 0.2C is 358mAh/g, the reversible specific capacity under 2C is 294mAh/g, and the reversible specific capacity under 5C is 251 mAh/g. The comprehensive leaching rate of the valuable metals on the positive electrode is 99.7 percent.
Example 3:
putting 100g of waste lithium ion battery black powder (same as example 1) into 300ml of perchloric acid, stirring and reacting for 4 hours at 0 ℃, and carrying out solid-liquid separation; the obtained filtrate is reserved for standby;
uniformly mixing the obtained powder materials in a mixer, and placing the mixture in a granulator for secondary granulation, wherein the material D50 is controlled to be 100 mu m;
thirdly, placing the obtained material in a tubular furnace under the argon atmosphere, raising the temperature to 1000 ℃ at the normal pressure at the heating rate of 50 ℃/min, then carrying out vacuum-pumping treatment on the system to ensure that the pressure of the system is 20Pa, and naturally cooling after heat preservation for 2 hours;
fourthly, mixing the roasted material with a liquid-solid ratio of 5: 1, dispersing in deionized water for slurrying, performing suction filtration after stirring reaction for 4 hours, and placing filter residues in a liquid-solid ratio of 3: slurrying in 3M sulfuric acid solution of 1, stirring for reaction for 4 hours, carrying out suction filtration and washing, and combining the filtrate with the filtrate in the step I for measuring the metal content;
fifthly, drying, crushing, screening, shaping, demagnetizing and packaging the leached residues.
The black powder raw material adopted in this embodiment is powder obtained by manually detaching the battery and then manually peeling the anode powder of the positive and negative electrode sheets. After the treatment of the embodiment, the graphitization degree of the obtained material is 99%, the ash content is 0.005%, the reversible specific capacity under 0.2C is 367mAh/g, the reversible specific capacity under 2C is 303mAh/g, and the reversible specific capacity under 5C is 263 mAh/g. The comprehensive leaching rate of the valuable metals on the positive electrode is 99.6 percent.
Example 4:
firstly, 100g of waste lithium ion battery black powder (same as the example 1) is placed in 300ml of concentrated sulfuric acid and 50ml of concentrated nitric acid, stirred and reacted for 2 hours at the temperature of 0 ℃, and solid-liquid separation is carried out; the obtained filtrate is reserved for standby;
uniformly mixing the obtained powder materials in a mixer, and placing the mixture in a granulator for secondary granulation, wherein the material D50 is controlled to be 100 mu m;
thirdly, placing the obtained material in a tubular furnace under the argon atmosphere, raising the temperature to 1000 ℃ at the normal pressure at the heating rate of 50 ℃/min, then carrying out vacuum-pumping treatment on the system to ensure that the pressure of the system is 20Pa, and naturally cooling after heat preservation for 2 hours;
fourthly, mixing the roasted materials according to a liquid-solid ratio of 5: 1, dispersing in deionized water for slurrying, performing suction filtration after stirring reaction for 4 hours, and placing filter residues in a liquid-solid ratio of 3: slurrying in 4M sulfuric acid solution of 1, stirring for reaction for 4 hours, carrying out suction filtration and washing, and combining the filtrate with the filtrate in the step I for measuring the metal content;
fifthly, drying, crushing, screening, shaping, demagnetizing and packaging the leached residues.
The black powder raw material adopted in this embodiment is powder obtained by manually detaching the battery and then manually peeling the anode powder of the positive and negative electrode sheets. After the treatment of the embodiment, the graphitization degree of the obtained material is 99.2%, the ash content is 0.002%, the reversible specific capacity under 0.2C is 366mAh/g, the reversible specific capacity under 2C is 287mAh/g, and the reversible specific capacity under 5C is 251 mAh/g. The comprehensive leaching rate of the valuable metals on the positive electrode is 99.8 percent.
Example 5:
putting 100g of waste lithium ion battery black powder (same as example 1) into 400ml of perchloric acid, stirring and reacting for 2 hours at the temperature of 30 ℃, and carrying out solid-liquid separation; the obtained filtrate is reserved for standby;
uniformly mixing the obtained powder materials in a mixer, and placing the mixture in a granulator for secondary granulation, wherein the material D50 is controlled to be 50 microns;
thirdly, placing the obtained material in a tubular furnace under the argon atmosphere, raising the temperature to 1000 ℃ at the normal pressure at the heating rate of 30 ℃/min, then carrying out vacuum-pumping treatment on the system to ensure that the pressure of the system is 50Pa, and naturally cooling after heat preservation for 2 hours;
fourthly, mixing the roasted materials according to a liquid-solid ratio of 5: 1, dispersing in deionized water for slurrying, performing suction filtration after stirring reaction for 4 hours, and placing filter residues in a liquid-solid ratio of 3: slurrying in 5M sulfuric acid solution of 1, stirring for reaction for 4 hours, carrying out suction filtration and washing, and combining the filtrate with the filtrate in the step I for measuring the metal content;
fifthly, drying, crushing, screening, shaping, demagnetizing and packaging the leached residues.
The black powder raw material adopted in this embodiment is powder obtained by manually detaching the battery and then manually peeling the anode powder of the positive and negative electrode sheets. After the treatment of the embodiment, the graphitization degree of the obtained material is 99.5%, the ash content is 0.001%, the reversible specific capacity at 0.2C is 363mAh/g, the reversible specific capacity at 2C is 302mAh/g, and the reversible specific capacity at 5C is 248 mAh/g. The comprehensive leaching rate of the valuable metals on the positive electrode is 99.9 percent.
Example 6:
firstly, 100g of waste lithium ion battery black powder (same as the embodiment 1) is placed in 400ml of perchloric acid, stirred and reacted for 2 hours at the temperature of 30 ℃, and solid-liquid separation is carried out; the obtained filtrate is reserved for standby;
uniformly mixing the obtained powder materials in a mixer, and placing the mixture in a granulator for secondary granulation, wherein the material D50 is controlled to be 80 microns;
thirdly, placing the obtained material in a tubular furnace under the argon atmosphere, raising the temperature to 1200 ℃ at the normal pressure at the heating rate of 50 ℃/min, then carrying out vacuum-pumping treatment on the system to ensure that the pressure of the system is 10Pa, and naturally cooling after heat preservation for 2 hours;
fourthly, mixing the roasted material with a liquid-solid ratio of 5: 1, dispersing in deionized water for slurrying, performing suction filtration after stirring reaction for 4 hours, and placing filter residues in a liquid-solid ratio of 3: slurrying in 6M sulfuric acid solution of 1, stirring for reaction for 4 hours, carrying out suction filtration and washing, and combining the filtrate with the filtrate in the step I for measuring the metal content;
fifthly, drying, crushing, screening, shaping, demagnetizing and packaging the leached residues.
The black powder raw material adopted in this embodiment is powder obtained by manually detaching the battery and then manually peeling the anode powder of the anode plate and the cathode plate. After the treatment of the embodiment, the graphitization degree of the obtained material is 99.5%, the ash content is 0.001%, the reversible specific capacity at 0.2C is 368mAh/g, the reversible specific capacity at 2C is 321mAh/g, and the reversible specific capacity at 5C is 267 mAh/g. The comprehensive leaching rate of the valuable metals on the positive electrode is 99.9 percent.
Example 7:
putting 100g of waste lithium ion battery black powder (same as example 1) into 400ml of perchloric acid, stirring and reacting for 2 hours at the temperature of 30 ℃, and carrying out solid-liquid separation; the obtained filtrate is reserved for standby;
uniformly mixing the obtained powder materials in a mixer, and placing the mixture in a granulator for secondary granulation, wherein the material D50 is controlled to be 100 mu m;
thirdly, placing the obtained material in a tubular furnace under the argon atmosphere, raising the temperature to 1100 ℃ at the normal pressure at the heating rate of 20 ℃/min, vacuumizing the system to ensure that the pressure of the system is 500Pa, preserving the heat for 2 hours, and naturally cooling;
fourthly, mixing the roasted material with a liquid-solid ratio of 5: 1, dispersing in deionized water for slurrying, performing suction filtration after stirring reaction for 4 hours, and placing filter residues in a liquid-solid ratio of 3: slurrying in 3M sulfuric acid solution of 1, stirring for reaction for 4 hours, carrying out suction filtration and washing, and combining the filtrate with the filtrate in the step I for measuring the metal content;
fifthly, drying, crushing, screening, shaping, demagnetizing and packaging the leached residues.
The black powder raw material adopted in this embodiment is powder obtained by manually detaching the battery and then manually peeling the anode powder of the positive and negative electrode sheets. After the treatment of the embodiment, the graphitization degree of the obtained material is 99.6%, the ash content is 0.002%, the reversible specific capacity under 0.2C is 359mAh/g, the reversible specific capacity under 2C is 317mAh/g, and the reversible specific capacity under 5C is 248 mAh/g. The comprehensive leaching rate of the valuable metals on the positive electrode is 99.8 percent.
Example 8:
putting 100g of waste lithium ion battery black powder (same as example 1) into 1000ml of concentrated sulfuric acid, stirring and reacting for 4 hours at 60 ℃, and carrying out solid-liquid separation; the obtained filtrate is reserved for standby;
uniformly mixing the obtained powder materials in a mixer, and placing the mixture in a granulator for secondary granulation, wherein the material D50 is controlled to be 80 microns;
thirdly, placing the obtained material in a tubular furnace under the argon atmosphere, raising the temperature to 1200 ℃ at the normal pressure at the heating rate of 40 ℃/min, then carrying out vacuum-pumping treatment on the system to ensure that the pressure of the system is 100Pa, and naturally cooling after heat preservation for 2 hours;
fourthly, mixing the roasted material with a liquid-solid ratio of 5: 1, dispersing in deionized water for slurrying, performing suction filtration after stirring reaction for 4 hours, and placing filter residues in a liquid-solid ratio of 3: slurrying in 4M sulfuric acid solution of 1, stirring for reaction for 4 hours, carrying out suction filtration and washing, and combining the filtrate with the filtrate in the step I for measuring the metal content;
fifthly, drying, crushing, screening, shaping, demagnetizing and packaging the leached residues.
The black powder raw material adopted in this embodiment is powder obtained by manually detaching the battery and then manually peeling the anode powder of the positive and negative electrode sheets. After the treatment of the embodiment, the graphitization degree of the obtained material is 96.8%, the ash content is 0.015%, the reversible specific capacity at 0.2C is 351mAh/g, the reversible specific capacity at 2C is 299mAh/g, and the reversible specific capacity at 5C is 249 mAh/g. The comprehensive leaching rate of the positive valuable metal is 99.2%.
Comparative example 1:
compared with the example 2, the difference is only that the following components are not subjected to oxidation intercalation, and specifically:
putting 100g of waste lithium ion battery black powder (powder obtained by manually stripping the anode powder and the cathode powder of a positive plate and a negative plate after manually disassembling the battery) into a mixer, uniformly mixing, putting into a granulator for secondary granulation, and controlling the material D50 to be 60 mu m;
secondly, placing the obtained material in a tubular furnace under the argon atmosphere, heating to 800 ℃ at the normal pressure at the heating rate of 50 ℃/min, vacuumizing the system to enable the pressure of the system to be 50Pa, preserving heat for 4 hours, and naturally cooling;
thirdly, mixing the roasted materials according to a liquid-solid ratio of 5: 1, dispersing in deionized water for slurrying, performing suction filtration after stirring reaction for 4 hours, and placing filter residues in a liquid-solid ratio of 3: pulping in 1M sulfuric acid solution, stirring for 4 hr, suction filtering, washing, and retaining the filtrate for measuring metal content.
And fourthly, drying, crushing, screening, shaping, demagnetizing and packaging the leached residues.
The SEM of the obtained material is shown in figure 6, and the obtained graphite material is obvious in particle shape and has no obvious layered structure, which shows that the graphite is not stripped without the oxidation intercalation treatment. The graphitization degree of the material is 87 percent, the ash content is 2.7 percent, the reversible specific capacity under 0.2C is 331mAh/g, the reversible specific capacity under 2C is 191mAh/g, and the reversible specific capacity under 5C is 79 mAh/g. The comprehensive leaching rate of the valuable metals of the positive electrode is 92.5 percent.
Comparative example 2:
the difference compared with example 2 is essentially that no granulation is carried out
Putting 100g of waste lithium ion battery black powder (powder obtained by manually stripping the anode powder of an anode plate and a cathode plate after batteries are manually disassembled) into 400ml of concentrated sulfuric acid, stirring and reacting for 4 hours at 20 ℃, and performing solid-liquid separation;
secondly, placing the obtained powder material in a tube furnace under the argon atmosphere, heating to 800 ℃ at the heating rate of 50 ℃/min under normal pressure, vacuumizing the system to enable the pressure of the system to be 50Pa, preserving heat for 4 hours, and naturally cooling;
thirdly, mixing the roasted materials according to a liquid-solid ratio of 5: 1, dispersing in deionized water for slurrying, performing suction filtration after stirring reaction for 4 hours, and placing filter residues in a liquid-solid ratio of 3: 1, slurrying in 2M sulfuric acid solution, stirring and reacting for 4 hours, carrying out suction filtration and washing, and mixing the filtrate with the step I to determine the metal content.
And fourthly, drying, crushing, screening, shaping, demagnetizing and packaging the leached residues.
The graphitization degree of the obtained material is 90%, the ash content is 0.04%, the reversible specific capacity under 0.2C is 341mAh/g, the reversible specific capacity under 2C is 171mAh/g, and the reversible specific capacity under 5C is 90 mAh/g. The comprehensive leaching rate of the positive valuable metal is 99.2%. The material is not granulated, the contact between the anode material and the cathode material is not tight, so that the catalytic action of the catalytic element in the anode powder on the amorphous carbon is insufficient, the purity of the obtained material is high, but the graphitization degree is not ideal, and the quick charging performance of the material is influenced.
Comparative example 3:
compared to example 1, the only difference is that the acid concentration during the oxidation treatment is lower (dilute acid), specifically:
putting 100g of waste lithium ion battery black powder (powder obtained by manually stripping the anode powder of an anode plate and a cathode plate after manually disassembling the battery) into 400ml of 2M dilute sulfuric acid, stirring and reacting for 4 hours at 20 ℃, and performing solid-liquid separation;
uniformly mixing the obtained powder materials in a mixer, and placing the mixture in a granulator for secondary granulation, wherein the material D50 is controlled to be 50 microns;
thirdly, placing the obtained material in a tubular furnace in nitrogen atmosphere, raising the temperature to 1000 ℃ at a temperature rise speed of 30 ℃/min under normal pressure, vacuumizing the system to make the pressure of the system 100Pa, preserving heat for 4 hours, and naturally cooling;
fourthly, mixing the obtained materials according to a liquid-solid ratio of 5: 1, dispersing in deionized water for slurrying, performing suction filtration after stirring reaction for 4 hours, and placing filter residues in a liquid-solid ratio of 3: 1, slurrying in 2M sulfuric acid solution, carrying out suction filtration and washing after stirring reaction for 4 hours, and combining filtrate with the oxidation treatment solution in the step I for measuring the metal content;
fifthly, drying, crushing, screening, shaping, demagnetizing and packaging the leached residues.
The graphitization degree of the obtained material is 91%, the ash content is 0.039%, the reversible specific capacity at 0.2C is 321mAh/g, the reversible specific capacity at 2C is 112mAh/g, and the reversible specific capacity at 5C is 53 mAh/g. The material is treated by dilute acid, so that intercalation treatment of graphite cannot be realized, and the rate capability of the material is influenced. The comprehensive leaching rate of the positive valuable metal is 93.6%.
Comparative example 4:
compared with example 1, the difference is that the atmospheric pressure heat treatment is adopted
Putting 100g of waste lithium ion battery black powder (powder obtained by manually stripping the anode powder of a positive electrode sheet and the cathode powder of a negative electrode sheet after manually disassembling the battery) into 500ml of concentrated sulfuric acid, stirring and reacting for 2 hours at 0 ℃, and performing solid-liquid separation;
uniformly mixing the obtained powder materials in a mixer, and placing the mixture in a granulator for secondary granulation, wherein the material D50 is controlled to be 50 microns;
thirdly, placing the obtained material in a tubular furnace in nitrogen atmosphere, raising the temperature to 1000 ℃ at the temperature rise speed of 30 ℃/min under normal pressure, preserving the temperature for 4 hours, and naturally cooling;
fourthly, mixing the obtained materials according to a liquid-solid ratio of 5: 1, dispersing in deionized water for slurrying, performing suction filtration after stirring reaction for 4 hours, and placing filter residues in a liquid-solid ratio of 3: pulping in 2M sulfuric acid solution of 1, performing suction filtration and washing after stirring and reacting for 4 hours, and combining filtrate with oxidation treatment solution in the step I for measuring metal content;
fifthly, drying, crushing, screening, shaping, demagnetizing and packaging the leached residues.
The graphitization degree of the obtained material is 88 percent, the ash content is 0.01 percent, the reversible specific capacity under 0.2C is 343mAh/g, the reversible specific capacity under 2C is 162mAh/g, and the reversible specific capacity under 5C is 84 mAh/g. Therefore, the normal pressure heat treatment is adopted, and the method has no positive effect on improving the graphitization degree of the material. The comprehensive leaching rate of the valuable metals of the positive electrode is 92.3 percent.
Comparative example 5:
compared with example 1, the difference is that potassium permanganate is used as the oxidizing agent
Putting 100g of waste lithium ion battery black powder into 1000ml of solution dissolved with 10g of potassium permanganate, stirring and reacting for 4 hours at the temperature of 60 ℃, and carrying out solid-liquid separation; the obtained filtrate is reserved for standby;
uniformly mixing the obtained powder materials in a mixer, and placing the mixture in a granulator for secondary granulation, wherein the material D50 is controlled to be 80 microns;
thirdly, placing the obtained material in a tubular furnace under the argon atmosphere, raising the temperature to 1200 ℃ at the normal pressure at the heating rate of 50 ℃/min, then carrying out vacuum-pumping treatment on the system to ensure that the pressure of the system is 50Pa, and naturally cooling after heat preservation for 2 hours;
fourthly, mixing the roasted material with a liquid-solid ratio of 5: 1, dispersing in deionized water for slurrying, performing suction filtration after stirring reaction for 4 hours, and placing filter residues in a liquid-solid ratio of 3: slurrying in 4M sulfuric acid solution of 1, stirring for reaction for 4 hours, carrying out suction filtration and washing, and combining the filtrate with the filtrate in the step I for measuring the metal content;
fifthly, drying, crushing, screening, shaping, demagnetizing and packaging the leached residues.
The black powder raw material adopted in this embodiment is powder obtained by manually detaching the battery and then manually peeling the anode powder of the positive and negative electrode sheets. After treatment, the graphitization degree of the obtained material is 92%, the ash content is 0.087%, the reversible specific capacity under 0.2C is 332mAh/g, the reversible specific capacity under 2C is 121mAh/g, and the reversible specific capacity under 5C is 54 mAh/g. The comprehensive leaching rate of the positive valuable metal is 94%.
Comparative example 6: with oxidation conditions outside the preferred range
Putting 100g of waste lithium ion battery black powder into 300ml of concentrated sulfuric acid, stirring and reacting for 6 hours at 80 ℃, and carrying out solid-liquid separation; the obtained filtrate is reserved for standby;
uniformly mixing the obtained powder materials in a mixer, and placing the mixture in a granulator for secondary granulation, wherein the material D50 is controlled to be 100 mu m;
thirdly, placing the obtained material in a tubular furnace under the argon atmosphere, raising the temperature to 1000 ℃ at the normal pressure at the heating rate of 50 ℃/min, then carrying out vacuum-pumping treatment on the system to ensure that the pressure of the system is 20Pa, and naturally cooling after heat preservation for 2 hours;
fourthly, mixing the roasted material with a liquid-solid ratio of 5: 1, dispersing in deionized water for slurrying, performing suction filtration after stirring reaction for 4 hours, and placing filter residues in a liquid-solid ratio of 3: slurrying in 4M sulfuric acid solution of 1, stirring for reaction for 4 hours, carrying out suction filtration and washing, and combining the filtrate with the filtrate in the step I for measuring the metal content;
fifthly, drying, crushing, screening, shaping, demagnetizing and packaging the leached residues.
The black powder raw material adopted in this embodiment is powder obtained by manually detaching the battery and then manually peeling the anode powder of the positive and negative electrode sheets. After treatment, the graphitization degree of the obtained material is 98%, the ash content is 0.042%, the reversible specific capacity under 0.2C is 322mAh/g, the reversible specific capacity under 2C is 155mAh/g, and the reversible specific capacity under 5C is 78 mAh/g. The comprehensive leaching rate of the positive valuable metal is 94%.
Comparative example 7: using a range outside the preferred secondary particle size
Putting 100g of waste lithium ion battery black powder into 500ml of concentrated sulfuric acid, stirring and reacting for 2 hours at the temperature of 0 ℃, and carrying out solid-liquid separation; the obtained filtrate is reserved for standby;
uniformly mixing the obtained powder materials in a mixer, and placing the mixture in a granulator for secondary granulation, wherein the material D50 is controlled to be 120 mu m;
thirdly, placing the obtained material in a tubular furnace under the nitrogen atmosphere, raising the temperature to 1000 ℃ at the normal pressure at the heating rate of 30 ℃/min, then carrying out vacuum-pumping treatment on the system to ensure that the pressure of the system is 100Pa, and naturally cooling after heat preservation for 4 hours;
fourthly, mixing the obtained materials according to a liquid-solid ratio of 5: 1, dispersing in deionized water for slurrying, performing suction filtration after stirring reaction for 4 hours, and placing filter residues in a liquid-solid ratio of 3: 1, adding 2M sulfuric acid solution into the filtrate obtained in the step I, uniformly mixing, stirring for reacting for 4 hours, performing suction filtration and washing, and measuring the content of valuable metals in the obtained filtrate;
fifthly, drying, crushing, screening, shaping, demagnetizing and packaging the leached residues.
The black powder raw material adopted in this embodiment is powder obtained by manually detaching the battery and then manually peeling the anode powder of the positive and negative electrode sheets. After treatment, the graphitization degree of the obtained material is 97%, the ash content is 0.2%, the reversible specific capacity under 0.2C is 322mAh/g, the reversible specific capacity under 2C is 123mAh/g, and the reversible specific capacity under 5C is 56 mAh/g. The comprehensive leaching rate of the positive valuable metal is 97.1 percent.
Comparative example 8: adopts a conventional heating mode
Putting 100g of waste lithium ion battery black powder into 400ml of perchloric acid, stirring and reacting for 2 hours at the temperature of 30 ℃, and carrying out solid-liquid separation; the obtained filtrate is reserved for standby;
uniformly mixing the obtained powder materials in a mixer, and placing the mixture in a granulator for secondary granulation, wherein the material D50 is controlled to be 100 mu m;
thirdly, placing the obtained material in a tubular furnace under the argon atmosphere, raising the temperature to 1100 ℃ at the normal pressure at the heating rate of 2 ℃/min, vacuumizing the system to ensure that the pressure of the system is 100Pa, preserving the heat for 2 hours, and naturally cooling;
fourthly, mixing the roasted material with a liquid-solid ratio of 5: 1, dispersing in deionized water for slurrying, performing suction filtration after stirring reaction for 4 hours, and placing filter residues in a liquid-solid ratio of 3: slurrying in 3M sulfuric acid solution of 1, stirring for reaction for 4 hours, carrying out suction filtration and washing, and combining the filtrate with the filtrate in the step I for measuring the metal content;
fifthly, drying, crushing, screening, shaping, demagnetizing and packaging the leached residues.
The black powder raw material adopted in this embodiment is powder obtained by manually detaching the battery and then manually peeling the anode powder of the positive and negative electrode sheets. After treatment, the graphitization degree of the obtained material is 91%, the ash content is 0.05%, the reversible specific capacity at 0.2C is 331mAh/g, the reversible specific capacity at 2C is 162mAh/g, and the reversible specific capacity at 5C is 82 mAh/g. The comprehensive leaching rate of the valuable metals on the positive electrode is 96.5 percent.
Comparative example 9: adopts the normal pressure heat treatment process
Putting 100g of waste lithium ion battery black powder into 400ml of perchloric acid, stirring and reacting for 2 hours at the temperature of 30 ℃, and carrying out solid-liquid separation; the obtained filtrate is reserved for standby;
uniformly mixing the obtained powder materials in a mixer, and placing the mixture in a granulator for secondary granulation, wherein the material D50 is controlled to be 50 microns;
thirdly, placing the obtained material in a tubular furnace under the argon atmosphere, heating to 1100 ℃ at the heating rate of 50 ℃/min under normal pressure, preserving the heat for 2 hours under normal pressure, and naturally cooling;
fourthly, mixing the roasted material with a liquid-solid ratio of 5: 1, dispersing in deionized water for slurrying, performing suction filtration after stirring reaction for 4 hours, and placing filter residues in a liquid-solid ratio of 3: slurrying in 3M sulfuric acid solution of 1, stirring for reaction for 4 hours, carrying out suction filtration and washing, and combining the filtrate with the filtrate in the step I for measuring the metal content;
fifthly, drying, crushing, screening, shaping, demagnetizing and packaging the leached residues.
The black powder raw material adopted in this embodiment is powder obtained by manually detaching the battery and then manually peeling the anode powder of the positive and negative electrode sheets. After treatment, the graphitization degree of the obtained material is 89%, the ash content is 0.08%, the reversible specific capacity under 0.2C is 321mAh/g, the reversible specific capacity under 2C is 159mAh/g, and the reversible specific capacity under 5C is 74 mAh/g. The comprehensive leaching rate of the positive valuable metal is 94%.
Comparative example 10: by heat treatment at a lower temperature
Putting 100g of waste lithium ion battery black powder into 500ml of concentrated sulfuric acid, stirring and reacting for 2 hours at the temperature of 0 ℃, and carrying out solid-liquid separation; the obtained filtrate is reserved for standby;
uniformly mixing the obtained powder materials in a mixer, and placing the mixture in a granulator for secondary granulation, wherein the material D50 is controlled to be 50 microns;
thirdly, placing the obtained material in a tubular furnace in nitrogen atmosphere, raising the temperature to 550 ℃ at the normal pressure at the heating rate of 30 ℃/min, vacuumizing the system to ensure that the pressure of the system is 100Pa, preserving the heat for 4 hours, and naturally cooling;
fourthly, mixing the obtained materials according to a liquid-solid ratio of 5: 1, dispersing in deionized water for slurrying, performing suction filtration after stirring reaction for 4 hours, and placing filter residues in a liquid-solid ratio of 3: 1, adding 2M sulfuric acid solution into the filtrate obtained in the step I, uniformly mixing, stirring for reacting for 4 hours, performing suction filtration and washing, and measuring the content of valuable metals in the obtained filtrate;
fifthly, drying, crushing, screening, shaping, demagnetizing and packaging the leached residues.
The black powder raw material adopted in this embodiment is powder obtained by manually detaching the battery and then manually peeling the anode powder of the positive and negative electrode sheets. After treatment, the graphitization degree of the obtained material is 89%, the ash content is 0.67%, the reversible specific capacity under 0.2C is 331mAh/g, the reversible specific capacity under 2C is 173mAh/g, and the reversible specific capacity under 5C is 59 mAh/g. The comprehensive leaching rate of the valuable metals on the positive electrode is 95 percent.
Claims (7)
1. A combined treatment method for black powder of waste lithium ion batteries is characterized by comprising the following steps:
step 1:
putting the waste lithium ion battery black powder into strong oxidizing acid liquor for oxidation treatment, and then carrying out solid-liquid separation to obtain oxidation treatment powder and oxidation treatment liquid; the waste lithium ion battery black powder is a mixture of anode powder and cathode powder of a waste battery; the strong oxidizing acid solution is at least one of concentrated sulfuric acid, concentrated nitric acid and perchloric acid; the oxidation temperature is 0-60 ℃, and the oxidation time is 0.5-4 h;
step 2:
granulating the oxidized powder; obtaining secondary particles; wherein the secondary particles have a D50= 18-100 μm;
and step 3:
heating the secondary particles to 600-1200 ℃ at a heating rate of 20-50 ℃/min, and roasting at a heat preservation pressure of 10-500 Pa;
and 4, step 4:
soaking the roasted material in water and then performing acid leaching treatment; leaching residues of acid leaching are recovered graphite; mixing the obtained leachate with the oxidation treatment solution of step 1, and recovering the positive electrode material.
2. The joint treatment method of the black powder of the waste lithium ion batteries according to claim 1, wherein the positive electrode powder is one or a mixture of more of lithium ferrate, lithium manganate, ternary lithium cobalt phosphate.
3. The combined treatment method of the black powder of the waste lithium ion batteries according to claim 1, wherein the negative electrode powder is graphite-based natural or artificial graphite negative electrode powder.
4. The joint treatment method of the black powder of the waste lithium ion batteries according to claim 1, wherein the liquid-solid ratio of the strong oxidizing acid liquid to the black powder of the waste lithium ion batteries is 3-10 mL/g.
5. The joint treatment method of the black powder of the waste lithium ion batteries according to claim 1, wherein the atmosphere in the sintering process is a non-oxygen atmosphere.
6. The joint treatment method of the black powder of the waste lithium ion batteries according to claim 1, wherein the atmosphere in the sintering process is one or more of nitrogen, argon, hydrogen and helium.
7. The combined treatment method of the black powder of the waste lithium ion batteries according to claim 1, wherein the acid solution adopted in the acid leaching process is at least one of hydrochloric acid, sulfuric acid and nitric acid; the concentration is 2-6M;
or, the acid liquor in the acid leaching process is the oxidation treatment liquid in the step 1.
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