CN111477990B - Method for recycling waste positive pole piece of lithium ion power battery - Google Patents
Method for recycling waste positive pole piece of lithium ion power battery Download PDFInfo
- Publication number
- CN111477990B CN111477990B CN202010584131.4A CN202010584131A CN111477990B CN 111477990 B CN111477990 B CN 111477990B CN 202010584131 A CN202010584131 A CN 202010584131A CN 111477990 B CN111477990 B CN 111477990B
- Authority
- CN
- China
- Prior art keywords
- leaching
- agent
- acid solution
- power battery
- positive pole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0423—Halogenated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0438—Nitric acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- 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
-
- 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
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- 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
Abstract
The invention provides a method for recovering a waste positive pole piece of a lithium ion power battery, which comprises the following steps: s1, cutting the waste positive pole piece of the lithium ion power battery to obtain a cut material; s2, immersing the cut material into a stripping agent for stripping treatment, then performing screening treatment below the liquid level, and separating oversize products to obtain a liquid-solid mixture; s3, adding a leaching agent into the liquid-solid mixture obtained in the step S2, and performing primary soaking treatment to obtain a first mixed system; s4, adding a leaching auxiliary agent into the first mixed system, and carrying out second soaking treatment to obtain a second mixed system; and S5, filtering the second mixed system to obtain the metal salt solution and the leaching residue of the anode material, and respectively recovering the metal salt solution and the leaching residue. The method can realize the recovery of the positive pole piece or all components of the waste lithium ion battery through a simplified recovery process, provides a new process route with short flow and high recovery rate, and can be suitable for the recovery of various lithium batteries.
Description
Technical Field
The invention belongs to the field of environmental protection and comprehensive utilization of resources, and particularly relates to a method for recycling a waste positive pole piece of a lithium ion power battery.
Background
With the popularization of electric vehicles, the number of power lithium batteries is increasing. However, after 3-7 years of use, lithium batteries are scrapped, and a large number of power lithium batteries have entered the scrapping period in recent years. The lithium ion battery contains volatile and easily-decomposed fluorine-containing electrolyte and heavy metal elements such as copper, cobalt, nickel, manganese and the like, and is easy to cause environmental problems and harm to human health if not properly treated after being discarded. In addition, aluminum, copper, lithium, cobalt, nickel, manganese, electrolyte and the like in the waste lithium ion battery are important valuable and strategic resources. The recycling of the lithium ion battery has three meanings of environment, economy and strategy.
The existing lithium battery recovery technology mainly comprises a pyrometallurgical technology and a hydrometallurgical technology. The pyrometallurgical technique has the characteristics of short process flow and simple operation, but the pyrometallurgical technique has high equipment investment, a large amount of waste gas is generated in the treatment process, and part of lithium element is discharged along with the waste gas, so the recovery efficiency of lithium by the pyrometallurgical technique is not high, and in addition, the pyrometallurgical technique needs to separate and recover nickel, cobalt, lithium and other elements by means of a further hydrometallurgical technique, which is described in the following patent documents: CN 201710392471 a recycling treatment process of waste batteries containing nickel and cobalt and CN 201711272420 a method for extracting lithium from slag generated by recovering lithium batteries by a pyrogenic process. The hydrometallurgical process has the advantage of high recovery. However, hydrometallurgical technology relies on complex pretreatment processes to enrich electrode materials by multiple crushing, grinding, multiple size sieving, electromagnetic sorting, density sorting, and the metals copper, aluminum can only be recovered in powder form, as described in the following patent documents: the method comprises a waste power lithium battery recovery method of CN 201811103327 and a lithium battery recovery process of CN 201811053034. The recovery process can be simplified by stripping the electrode sheet, and the current stripping technology needs to introduce an external alkaline substance or an organic solvent to realize stripping, which is easy to cause secondary pollution, as described in the following patent documents: "CN 101818251 method for recovering cobalt and lithium from waste lithium ion battery" and "CN 102703706 method for recovering valuable metal from waste lithium cobalt oxide battery". However, the scheme proposed by the patent document "recovery method for stripping and leaching waste lithium ion batteries in one step" avoids the introduction of foreign substances, but copper and aluminum finally enter filter residues, an additional process is required for separating and recovering the copper and the aluminum, and the method cannot realize the separation and recovery of the diaphragm, the electrolyte and the shell.
Disclosure of Invention
In order to solve the above problems, the present disclosure provides a method for recycling a waste positive electrode plate of a lithium ion power battery.
In order to solve the technical problem, the technical scheme provided by the disclosure is as follows:
a method for recycling waste positive pole pieces of a lithium ion power battery sequentially comprises the following steps:
stripping the waste positive pole piece of the lithium ion power battery by using a stripping agent, and screening and separating to respectively obtain an aluminum foil and a liquid-solid mixture comprising an electrode material which is not dissolved yet and a solution in which part of the electrode material is dissolved;
adding a leaching agent into the liquid-solid mixture for leaching treatment;
and (4) continuously adding a leaching auxiliary agent into the system obtained by the leaching treatment of the leaching agent for further leaching treatment, and finally filtering and separating to respectively obtain recovered products.
In the above method for recycling waste positive electrode pieces of a lithium ion power battery, as a preferred embodiment, the method comprises the following steps:
s1, cutting the waste positive pole piece of the lithium ion power battery to obtain a cut material;
s2, immersing the cut material obtained in the step S1 into a stripping agent for stripping treatment, and then carrying out screening treatment to separate out oversize products, namely aluminum foils, so as to obtain a liquid-solid mixture; the liquid-solid mixture comprises electrode materials which are not dissolved yet and solution in which part of the electrode materials are dissolved;
s3, adding a leaching agent into the liquid-solid mixture obtained in the step S2, and performing primary soaking treatment to obtain a first mixed system;
s4, adding a leaching auxiliary agent into the first mixed system obtained in the step S3, and performing second soaking treatment to obtain a second mixed system;
and S5, filtering the second mixed system obtained in the step S4 to obtain a metal salt solution of the positive electrode material and leaching residues, and respectively recovering the metal salt solution and the leaching residues.
In the above method for recycling the waste positive electrode sheet of the lithium ion power battery, as a preferred embodiment, in step S1, the size of the cut material is 0.5-5 cm (e.g., 0.8cm, 1.2cm, 1.5cm, 2cm, 2.5cm, 3cm, 3.5cm, 4cm, 4.5cm, etc.).
In the method for recycling the waste positive pole piece of the lithium ion power battery, the step S2 is to strip the cut waste positive pole piece of the lithium ion power battery, and after the stripping treatment, the particle size of the electrode material is reduced, while the size of the aluminum foil is not changed, so that the screening separation is possible.
In the above method for recycling a waste positive electrode sheet of a lithium ion power battery, as a preferred embodiment, in step S2, the stripping agent is selected from any one or a mixture of a citric acid solution, an acetic acid solution, a phosphoric acid solution, a hydrochloric acid solution, a sulfuric acid solution, a nitric acid solution, a glutaric acid solution, and a perchloric acid solution; preferably, the concentration of the stripping agent is 1-30wt.% (such as 2wt.%, 5wt.%, 8wt.%, 10wt.%, 12wt.%, 15wt.%, 18wt.%, 20wt.%, 22wt.%, 24wt.%, 26 wt.%, 28wt.%, etc.). Experiments prove that the concentration of the stripping agent in the step is higher than 40wt.%, which can cause the aluminum foil to be completely dissolved and is not beneficial to recycling the aluminum foil; for example, about 80% of aluminum can be recovered at a concentration of 30wt.%, but the aluminum dissolution rate is high, and finally, an additional process is required to remove aluminum, which complicates the process; if the acid concentration is less than 25%, the leaching rate of aluminum is only about 1.4%, but if the stripping agent is more than 25%, the leaching rate of aluminum begins to increase rapidly. More preferably, the concentration of the stripping agent is 1 to 25wt.% (such as 1.5wt.%, 4wt.%, 7wt.%, 12wt.%, 16wt.%, 21wt.%, 24wt.% and the like), which can simplify the subsequent processes; further, the concentration of the stripping agent is 1 to 10wt.% (e.g., 1.5wt.%, 2wt.%, 3wt.%, 4wt.%, 5wt.%, 6wt.%, 7wt.%, 8wt.%, 9wt.%, 9.5wt.%, etc.), which can further simplify the subsequent processes.
In the above method for recycling the waste positive electrode sheet of the lithium ion power battery, as a preferred embodiment, in step S2, after the stripping agent is added, the liquid-solid ratio of the system is 5-50:1 (the liquid-solid ratio is the mass ratio of the stripping agent used in the stripping treatment to the waste positive electrode sheet of the lithium ion power battery cut in step S1, such as 10:1, 15:1, 20:1, 30:1, 40:1, etc.).
In the above method for recycling waste positive electrode pieces of a lithium ion power battery, as a preferred embodiment, in step S2, the battery pieces obtained after cutting are immersed in a stripping agent and then subjected to vibration or stirring treatment, that is, the stripping treatment process may be accompanied by vibration or stirring treatment, so that the stripping treatment is smoother and the stripping is more thorough; more preferably, the shaking or stirring treatment time is 5-15min (such as 6min, 8min, 10min, 12min, 14min, etc.).
In the above method for recovering the waste positive electrode sheet of the lithium ion power battery, as a preferred embodiment, in step S2, the temperature of the reaction system is maintained at 20 to 80 ℃ (for example, 25 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 75 ℃ and the like).
In the above method for recovering a discarded positive electrode sheet of a lithium ion power battery, as a preferred embodiment, in step S2, the screening process is performed below the liquid level.
In the above method for recovering a waste positive electrode sheet of a lithium ion power battery, as a preferred embodiment, step S2 further includes: and cleaning the oversize product to obtain clean aluminum foil and washing water.
In the above method for recovering a waste positive electrode sheet of a lithium ion power battery, as a preferred embodiment, in step S2, the washing water obtained by washing the aluminum foil is returned to the liquid-solid mixture obtained in step S2.
In the above method for recovering a waste positive electrode sheet of a lithium ion power battery, as a preferred embodiment, step S2 further includes: a protective agent is also added in the stripping treatment process to inhibit aluminum leaching and/or improve the quality of recovered aluminum; more preferably, the protective agent comprises an inorganic protective agent and/or an organic protective agent, the inorganic protective agent being selected from: any one or a mixture of chromate, inorganic copper salt, nitrate, molybdate, tungstate, phosphate and hydrogen phosphate; the organic protective agent is an organic compound with one or more active groups containing heteroatoms such as N, S, O and P, and further can be selected from: one or a mixture of polymethacrylic acid, zinc gluconate, crystal violet dye, glutaric acid, 2, 3-diaminonaphthalene, sodium dodecyl benzene sulfonate, carboxyethyl cellulose, hydroxy flavone, quaternary ammonium bromide, diethylenetriamine, sodium benzoate, melamine and tween 20. The protective agent added in the step S2 can inhibit aluminum leaching, reduce the leaching rate of aluminum, protect aluminum from being oxidized, and ensure low oxygen content, good surface gloss and high quality of the recovered aluminum.
In the above method for recycling the waste positive electrode plate of the lithium ion power battery, as a preferred embodiment, in step S2, the protective agent is a soluble inorganic copper salt; the soluble inorganic copper salt is added in an amount of Cu2+Calculated as 200-1000ppm (e.g., 250ppm, 300ppm, 400ppm, 500ppm, 600ppm, 700ppm, 800ppm, 900ppm, etc.).
In the above method for recycling the waste positive electrode sheet of the lithium ion power battery, as a preferred embodiment, in step S2, the protective agent is sodium benzoate, and the amount of the sodium benzoate added is 200-700ppm (for example, 250ppm, 300ppm, 400ppm, 500ppm, 600ppm, 650ppm, etc.).
In the above method for recycling the waste positive electrode plate of the lithium ion power battery, as a preferred embodiment, in step S2, the protective agent is melamine, and the addition amount of the melamine is 1ppm or more; more preferably 1-100ppm (such as 20ppm, 40ppm, 80ppm, 90ppm, etc.).
In the above method for recycling a waste positive electrode sheet of a lithium ion power battery, as a preferred embodiment, in step S2, the protective agent is tween 20, and the addition amount of tween 20 is 10 to 100ppm (for example, 20ppm, 30ppm, 50ppm, 70ppm, 90ppm, etc.).
In the above method for recycling the waste positive electrode sheet of the lithium ion power battery, as a preferred embodiment, in step S3, the leaching agent is selected from any one or a mixture of a citric acid solution, an acetic acid solution, a phosphoric acid solution, a hydrochloric acid solution, a sulfuric acid solution, a nitric acid solution, a glutaric acid solution, and a perchloric acid solution.
In the above method for recovering the waste positive electrode plate of the lithium ion power battery, as a preferred embodiment, in step S3, the adding of the leaching agent makes the solute concentration of the leaching agent reach 10-40 wt% (e.g., 12wt.%, 15wt.%, 20wt.%, 25wt.%, 30wt.%, 35wt.%, 38 wt.%). More preferably, in step S3, the addition of the leaching agent results in a leaching agent solute concentration of 20-35 wt.%.
In the above method for recycling waste positive electrode pieces of lithium ion power batteries, as a preferred embodiment, in step S3, the leaching agent is added in a molar ratio of (Ni + Co + Mn +2Li): H+And (c) =1:2-10 (e.g., 1:2.02, 1:2.2, 1:2.25, 1:2.3, 1:2.4, 1:2.5, 1:8, 1:10, etc.).
In the above method for recycling waste positive electrode pieces of a lithium ion power battery, as a preferred embodiment, in step S3, after the leaching agent is added, the time of the first soaking treatment is 10 to 120min (for example, 20min, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, and the like).
In the above method for recovering the waste positive electrode sheet of the lithium ion power battery, as a preferred embodiment, in step S3, the reaction temperature is maintained at 20 to 100 ℃ (for example, 25 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 95 ℃ and the like). In practice, the temperature rise is mainly to increase the leaching speed, but needs to be adjusted according to the type of acid used, for example, hydrochloric acid and acetic acid are volatile, and the corresponding temperature needs to be slightly reduced.
In the above method for recycling the waste positive electrode plate of the lithium ion power battery, as a preferred embodiment, in step S4, the leaching aid is selected from one or a mixture of more of hydrogen peroxide, sodium sulfite, sulfur dioxide, hydrogen sulfide, sodium chloride and potassium chloride.
In the above method for recycling waste positive electrode pieces of lithium ion power batteries, as a preferred embodiment, in step S4, the concentration of the leaching aid added to the first mixed system obtained in step S3 is 6 to 35wt.% (for example, 8wt.%, 15%, 20wt.%, 25wt.%, 28wt.%, 30wt.%, 32wt.%, 34 wt.%).
In the above method for recycling the waste positive electrode plate of the lithium ion power battery, as a preferred embodiment, in step S4, after the leaching aid is added, the time of the second soaking treatment is 30 to 150min (for example, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min, 130min, 140min, and the like).
In the above method for recovering a waste positive electrode sheet of a lithium ion power battery, as a preferred embodiment, step S5 further includes: adjusting the metal salt solution of the cathode material to the molar ratio of Ni, Co and Mn (such as 1:1:1, 5:2:3, 3:1:1, 8:1: 1) required by the production of a cathode precursor, and then sequentially carrying out precipitation, centrifugation, washing and filtration to finally obtain (Ni, Co, Mn) OH2Product and filtrate; mixing Na2CO3Adding to the filtrate to recover Li2CO3。
Compared with the prior art, the beneficial effects of the present disclosure include but are not limited to:
1) the method can recover the aluminum of the waste positive pole piece of the lithium ion power battery in the form of the aluminum foil, and the recovered aluminum quantity is high;
2) the method can reduce the impurity content in the cobalt or/and nickel or/and manganese leaching solution, and reduce the generation amount of secondary waste in the impurity removal process;
3) the method can greatly improve the concentration of the cobalt or/and nickel or/and manganese leaching solution, thereby reducing the water consumption and avoiding generating wastewater.
Drawings
Fig. 1 shows a photograph of an aluminum foil obtained by peeling off a positive electrode sheet in step S1 of example 2 of the present disclosure using 5wt.% of a nitric acid solution/a glutaric acid solution/a perchloric acid solution (molar ratio 3:1: 1) for a waste positive electrode sheet of an NCM523 lithium ion power battery.
The graph in fig. 2 shows the positive electrode peel rate as a function of time at an acid concentration of 5wt.% for the positive electrode sheet of the NCM523 battery in example 4.
FIG. 3 is a photograph of an aluminum foil taken with a stripping treatment without (example 2) and with (300 ppm, example 8) copper ion protectant added, an SEM photograph and a corresponding X-ray spectroscopy analysis showing the effect of the presence of copper ions on the recovered aluminum foil.
FIG. 4 shows the leaching rate of aluminum as a function of the amount of sodium benzoate added (acid concentration 5%) in example 9.
FIG. 5 shows the aluminum leaching in example 9 as a function of the melamine addition (5% acid concentration).
FIG. 6 shows the change of the leaching rate of aluminum (acid concentration 5%) according to the amount of Tween 20 added in example 9.
Figure 7 shows the results of stripping and leaching of different types of pole pieces using the leaching process described in example 6.
Detailed Description
The following examples are presented to facilitate a better understanding of the present disclosure, but are not intended to limit the same.
The experimental procedures in the following examples are conventional unless otherwise specified.
The test materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
Example 1
1) Cutting the waste positive pole piece of the NCM523 lithium ion power battery, wherein the size of the cut waste positive pole piece of the lithium ion power battery is about 2 cm;
2) the cut pole pieces were added to a 3wt.% concentration of acetic acid/citric acid/sulfuric acid (molar ratio 1:1: 1) in the solution (i.e. the stripping agent), the solid-to-liquid ratio is 1:10, the temperature of the solution is kept at 50 ℃, the solution is stirred for 10min to separate the electrode material from the aluminum foil, and then the electrode material and the aluminum foil are sieved under water; washing the oversize product to recover aluminum foil, and returning the washing water to 3wt.% of stripping agent, wherein the aluminum recovery rate is 99.5%;
3) adding nitric acid (68 wt.%) to the remaining liquid-solid mixture of step 2) to give a system acid concentration of 30wt.%, by molar ratio (Ni + Co + Mn +2Li): H+Calculating by the ratio of 1:2.02, keeping the temperature at 30 ℃, and soaking for 1h under the condition of stirring;
4) adding 27.5wt.% hydrogen peroxide into the system obtained in the step 3), wherein the adding amount of the hydrogen peroxide is calculated according to the molar ratio (Ni + Co + Mn): H2O2Calculating by the ratio of 1:1.2, adding hydrogen peroxide, continuing to soak for 1h, and keeping the temperature at 50 ℃;
5) filtering the solution obtained in the step 4) after reaction to obtain a cobalt nickel manganese lithium salt solution and leaching residues (mainly used as a positive electrode binder and a conductive agent); and (3) cleaning the leached residues, combining the cleaning liquid with the cobalt nickel manganese lithium salt solution to obtain a cobalt nickel manganese lithium salt solution product, wherein the recovery rates of lithium, nickel, cobalt and manganese are respectively 98.6%, 99.7%, 98.6% and 99.2%.
Example 2
1) Cutting the waste positive pole piece of the NCM523 lithium ion power battery, wherein the size of the cut waste positive pole piece is about 2 cm;
2) the cut pole piece was added to a 5wt.% nitric acid solution/glutaric acid solution/perchloric acid solution (molar ratio 3:1: 1) in the method, the solid-to-liquid ratio is 1:10, the solution temperature is kept at 40 ℃, the solution is stirred for 10min to separate an electrode material from an aluminum foil, and then the electrode material and the aluminum foil are sieved under water; washing the oversize product to recover aluminum foil, and returning the washing water to 5wt.% of stripping agent solution, wherein the aluminum recovery rate is 99.2%;
3) adding a certain amount of concentrated hydrochloric acid (35 wt.%) to the liquid-solid mixture left in the step 2) to make the acid concentration of the system be 15wt.%, and adding the concentrated hydrochloric acid in a molar ratio of (Ni + Co + Mn +2Li): H+Calculating according to the ratio of 1:2.02, keeping the temperature at 25 ℃, and soaking for 1h under the condition of stirring;
4) adding sodium sulfite into the system obtained in the step 3), wherein the adding amount of the sodium sulfite is calculated according to the molar ratio (Ni + Co + Mn) of the sodium sulfite =1:0.6, and continuously soaking for 1.5h after the sodium sulfite is added, and keeping the temperature at 40 ℃;
5) filtering the solution obtained in the step 4) after reaction to obtain a cobalt nickel manganese lithium salt solution and leaching residues (mainly used as a positive electrode binder and a conductive agent); and (3) cleaning the leaching residues, combining the cleaning solution with the cobalt nickel manganese lithium salt solution to obtain a cobalt nickel manganese lithium salt solution product, wherein the recovery rates of lithium, nickel, cobalt and manganese are respectively 99.5%, 98.7%, 99.4% and 99.7%.
Example 3
1) Cutting the waste positive pole piece of the NCM622 lithium ion power battery, wherein the size of the cut positive pole piece is about 2 cm;
2) the cleaved monomer was added to a phosphoric acid solution/glutaric acid solution/nitric acid solution at a concentration of 10wt.% (molar ratio 4: 2: 1) in the solution, the solid-to-liquid ratio is 1:10, the solution temperature is kept at 50 ℃, the solution is stirred for 10min to separate the electrode material from the aluminum foil, and then the electrode material and the aluminum foil are sieved under water; cleaning the oversize product to recover aluminum foil, returning the cleaning water to the stripping agent solution, recovering aluminum at 94.2%,
3) adding a certain amount of concentrated sulfuric acid (98 wt.%)/nitric acid (68 wt.%) mixed solution to the liquid-solid mixture remaining from step 2) (molar ratio 1: 1) the acid concentration of the system was set to 30wt.%, and the amount added was determined by the molar ratio (Ni + Co + Mn +2Li): H+Calculating by the ratio of 1:2.02, keeping the temperature at 90 ℃, and soaking for 1h under the condition of stirring;
4) adding 27.5wt.% of hydrogen peroxide into the system obtained in the step 3), wherein the adding amount of the hydrogen peroxide is calculated according to the molar ratio (Ni + Co + Mn) and the ratio of hydrogen peroxide =1:1.4, continuously soaking for 1.5h after adding the hydrogen peroxide, and keeping the temperature at 40 ℃;
5) filtering the solution obtained in the step 4) after reaction to obtain a cobalt nickel manganese lithium salt solution and leaching residues (mainly used as a positive electrode binder and a conductive agent); and (3) cleaning the leached residues, combining the cleaning solution with the cobalt nickel manganese lithium salt solution to obtain a cobalt nickel manganese lithium salt solution product, wherein the recovery rates of lithium, nickel, cobalt and manganese are respectively about 100%, 98.1%, 99.4% and 95.7%.
Example 4
1) Cutting the waste positive pole piece of the cylindrical NCM523 (Cylinder NCM 523) lithium ion power battery, wherein the size of the cut waste positive pole piece is about 2 cm;
2) the cut monomers were added to a 5wt.% citric acid solution/glutaric acid solution/sulfuric acid solution (molar ratio 1:1: 3) in the solution, the solid-to-liquid ratio is 1:10, the solution temperature is kept at 50 ℃, the solution is stirred for 10min to separate the electrode material from the aluminum foil, and then the electrode material and the aluminum foil are sieved under water; cleaning the oversize product to recover aluminum foil, and returning the cleaning water to the stripping agent solution, wherein the recovery rate of aluminum is 94.2%; the graph in fig. 2 shows the positive electrode peel rate as a function of time at an acid concentration of 5wt.% for the positive electrode sheet of the NCM523 battery in example 4; as can be seen from the figure, the stripping speed of the positive electrode is extremely high, and the stripping can be finished within 1 min;
3) adding into the liquid-solid mixture left in the step 2)Adding concentrated sulfuric acid (98 wt.%)/nitric acid (68 wt.%) to obtain a mixed solution (molar ratio of 1: 1) to obtain an acid concentration of 30wt.%, and adding H at a molar ratio (Ni + Co + Mn +2Li): H2SO4Calculating according to the ratio of 1:1.01, keeping the temperature at 90 ℃, and soaking for 1h under the condition of stirring;
4) adding sodium sulfite into the system obtained in the step 3), wherein the adding amount of the sodium sulfite is calculated according to the molar ratio (Ni + Co + Mn) of the sodium sulfite =1:0.6, adding hydrogen peroxide, continuing to soak for 1.5h, and keeping the temperature at 40 ℃;
5) filtering the solution obtained in the step 4) after reaction to obtain a cobalt nickel manganese lithium salt solution and leaching residues (mainly used as a positive electrode binder and a conductive agent); and (3) cleaning the leaching residues, combining the cleaning solution with the cobalt nickel manganese lithium salt solution to obtain a cobalt nickel manganese lithium sulfate solution product, wherein the recovery rates of lithium, nickel, cobalt and manganese are respectively about 100%, 96.8%, 97.2% and 91.7%.
Example 5
1) Cutting the waste positive pole piece of the LMO (Soft-pack LMO) lithium ion power battery, wherein the size after cutting is about 2 cm;
2) the cut monomers were added to a 5wt.% citric acid solution/glutaric acid solution/sulfuric acid solution (molar ratio 1:1: 3) in the solution, the solid-to-liquid ratio is 1:10, the solution temperature is kept at 50 ℃, the solution is stirred for 10min to separate the electrode material from the aluminum foil, and then the electrode material and the aluminum foil are sieved under water; washing the oversize to recover aluminum foil, returning the washing water to 5wt.% of stripping agent solution, and achieving an aluminum recovery rate of 96.9%;
3) adding a certain amount of concentrated sulfuric acid (98 wt.%)/nitric acid (68 wt.%) mixed solution to the liquid-solid mixture remaining from step 2) (molar ratio 1: 1) the acid concentration of the system was set to 30wt.%, and the amount added was determined by the molar ratio (Ni + Co + Mn +2Li): H+Calculating by the ratio of 1:2.02, keeping the temperature at 90 ℃, and soaking for 1h under the condition of stirring;
4) introducing sulfur dioxide into the system obtained in the step 3), wherein the adding amount of the sulfur dioxide is calculated according to the molar ratio of Mn to the sulfur dioxide =1 to 0.6, adding hydrogen peroxide, continuing to soak for 1.5h, and keeping the temperature at 40 ℃;
5) filtering the solution obtained in the step 4) after reaction to obtain a cobalt nickel manganese lithium salt solution and leaching residues (mainly used as a positive electrode binder and a conductive agent); and (3) cleaning the leached residues, and combining the cleaning solution and the cobalt nickel manganese lithium salt solution to obtain a cobalt nickel manganese lithium salt solution product, wherein the recovery rates of lithium and manganese are respectively 96.2% and about 100%.
Example 6
1) Cutting the waste positive pole piece of the soft package NCM523 lithium ion power battery, wherein the size after cutting is about 2 cm;
2) the cut monomers were added to a 5wt.% citric acid solution/glutaric acid solution/sulfuric acid solution (molar ratio 1:1: 3) in the solution, the solid-to-liquid ratio is 1:10, the solution temperature is kept at 50 ℃, the solution is stirred for 10min to separate the electrode material from the aluminum foil, and then the electrode material and the aluminum foil are sieved under water; washing the oversize to recover aluminum foil, returning the washing water to 5wt.% of stripping agent solution, and achieving an aluminum recovery rate of 95.2%;
3) adding a certain amount of concentrated sulfuric acid (98 wt.%)/nitric acid (68 wt.%) mixed solution to the liquid-solid mixture remaining from step 2) (molar ratio 1: 1) the acid concentration of the system was set to 20wt.%, and the amount added was determined by the molar ratio (Ni + Co + Mn +2Li): H+Calculating by the ratio of 1:2.02, keeping the temperature at 65 ℃, and soaking for 1h under the condition of stirring;
4) introducing hydrogen sulfide into the system obtained in the step 3), wherein the adding amount of the hydrogen sulfide is calculated according to the molar ratio (Ni + Co + Mn) to the hydrogen sulfide =1:0.7, and continuously soaking for 1h after the hydrogen sulfide is added, and keeping the temperature at 50 ℃;
5) filtering the solution obtained in the step 4) after reaction to obtain a cobalt nickel manganese lithium salt solution and leaching residues (mainly used as a positive electrode binder and a conductive agent); and (3) cleaning the leached residues, combining the cleaning liquid with the cobalt nickel manganese lithium salt solution to obtain a cobalt nickel manganese lithium salt solution product, wherein the recovery rates of lithium, nickel, cobalt and manganese are respectively 99.5%, 98.7%, about 100% and about 100%, see fig. 7.
Example 7
1) Cutting the waste positive pole piece of the soft package NCM523 lithium ion power battery, wherein the size after cutting is about 2 cm;
2) the cut monomers were added to a 2wt.% citric acid solution/glutaric acid solution/sulfuric acid solution (molar ratio 1:1: 3) in the solution, the solid-to-liquid ratio is 1:10, the solution temperature is kept at 50 ℃, the solution is stirred for 5min to separate the electrode material from the aluminum foil, and then the electrode material and the aluminum foil are sieved under water; washing the oversize to recover aluminum foil, returning the washing water to 2wt.% of stripping agent solution, and achieving an aluminum recovery rate of 94.9%;
3) adding a certain amount of glutaric acid solution/sulfuric acid (molar ratio 1: 4) the solution was mixed so that the acid concentration of the system was 20wt.%, and the amount added was determined by the molar ratio (Ni + Co + Mn +2Li): H+Calculating by the ratio of 1:2.02, keeping the temperature at 25 ℃, and soaking for 10min under the condition of stirring;
4) adding 27.5wt.% hydrogen peroxide into the system obtained in the step 3), wherein the adding amount of the hydrogen peroxide is calculated according to the molar ratio (Ni + Co + Mn): H2O2Calculating by the ratio of 1:1.2, adding hydrogen peroxide, continuing to soak for 1.5h, and keeping the temperature at 50 ℃;
5) filtering the solution obtained in the step 4) after reaction to obtain a cobalt nickel manganese lithium salt solution and leaching residues (mainly used as a positive electrode binder and a conductive agent); and (3) cleaning the leached residues, combining the cleaning solution with the cobalt nickel manganese lithium salt solution to obtain a cobalt nickel manganese lithium salt solution product, wherein the recovery rates of lithium, nickel, cobalt and manganese are respectively about 100%, 98.3%, 99.8% and 99.1%.
Example 8
In this embodiment, compared with embodiment 2, there is only one difference, that is, the copper protective agent is added in the stripping process, specifically as follows:
1) cutting the waste positive pole piece of the NCM523 lithium ion power battery to obtain a cut positive pole piece with the size of about 2 cm;
2) the cut pole piece was added to a 5wt.% nitric acid/glutaric acid/perchloric acid solution (molar ratio 3:1: 1) adding copper sulfate (the concentration of copper ions in the added solution is 300 ppm) at a solid-to-liquid ratio of 1:10, keeping the temperature of the solution at 40 ℃, stirring for 10min to separate the electrode material from the aluminum foil, and sieving under water; washing the oversize product to recover aluminum foil, and returning the washing water to 5wt.% of stripping agent solution, wherein the aluminum recovery rate is 99.2%;
3) adding a certain amount of water to the liquid-solid mixture left in the step 2)Concentrated hydrochloric acid (35 wt.%), so that the acid concentration in the system is 15wt.%, and the addition is carried out in a molar ratio (Ni + Co + Mn +2Li): H+Calculating according to the ratio of 1:2.02, keeping the temperature at 25 ℃, and soaking for 1h under the condition of stirring;
4) adding sodium sulfite into the system obtained in the step 3), wherein the adding amount of the sodium sulfite is calculated according to the molar ratio (Ni + Co + Mn) of the sodium sulfite =1:0.6, and continuously soaking for 1.5h after the sodium sulfite is added, and keeping the temperature at 40 ℃;
5) filtering the solution obtained in the step 4) after reaction to obtain a cobalt nickel manganese lithium salt solution and leaching residues (mainly used as a positive electrode binder and a conductive agent); and (3) cleaning the leaching residues, combining the cleaning solution with the cobalt nickel manganese lithium salt solution to obtain a cobalt nickel manganese lithium salt solution product, wherein the recovery rates of lithium, nickel, cobalt and manganese are respectively 99.5%, 98.7%, 99.4% and 99.7%.
Referring to fig. 3, it can be seen that the upper part shows the effect when no copper ions are added, the surface of the aluminum foil is discolored, the oxygen content is high, and the lower part shows that the surface of the aluminum foil maintains the original color when 300ppm of copper is added, the oxygen content is low, which indicates that trace copper is deposited on the surface of the aluminum foil in the presence of copper, so as to inhibit the generation of aluminum oxide and improve the quality of the recovered aluminum foil; in other words, the addition of the copper ion protective agent reduces the oxygen content on the surface of the recovered aluminum foil, the recovered aluminum foil is brighter, the metal aluminum content is also high, and the quality of the recovered aluminum is improved.
Example 9
This example comprises a set of experiments, the only difference between the procedure and the process parameters compared to example 1 is that the protective agents were added separately during the stripping: sodium benzoate, melamine and tween 20. In the stripping process, the addition amount of the protective agent and the Al leaching rate are changed, as shown in fig. 4, 5 and 6; as can be seen from FIG. 4, trace benzoic acid is added as a protective agent in the stripping process, which is beneficial to reducing the leaching rate of aluminum and improving the quality of recovered aluminum foil and the adaptability of the process, and the optimal addition amount of sodium benzoate is 248 ppm; as can be seen from FIG. 5, the addition of trace melamine as a protective agent during the stripping process is beneficial to reducing the leaching rate of aluminum and improving the quality of the recovered aluminum foil and the adaptability of the process, and the optimal addition amount of melamine is 84 ppm; as can be seen from FIG. 6, the addition of trace amount of Tween 20 as a protective agent during the stripping process is beneficial to reducing the leaching rate of aluminum and improving the quality of the recovered aluminum foil and the adaptability of the process, and the optimal addition amount of Tween 20 is 100 ppm. As can be seen from the figure, the addition of a trace amount of protective agent is beneficial to inhibiting the leaching of aluminum in the stripping process, thereby improving the quality of recovered aluminum, reducing the concentration of aluminum entering a subsequent process and being beneficial to improving the quality of the salt solution for recovering cobalt, nickel, manganese and lithium.
Example 10
This example includes a set of experiments, which, compared to example 6, are different only in the battery electrode plates, which are: soft-package LMO positive pole piece (Soft-pack LMO), Soft-package Co/Ni-doped LMO (Soft-pack Co/Ni-dope LMO) positive pole piece, Soft-package Co-doped LMO (Soft-pack Co-dope LMO) positive pole piece, Soft-package Co/Ni-doped LMO II (Soft-pack Co/Ni-dope LMO II) positive pole piece, cylindrical NCM523 (Cylinder NCM 523) positive pole piece, hard-shell NCM523 (rigid NCM 523) positive pole piece, NCM622 (Catode NCM 622) scrapped positive pole piece
The recovery rates of the elements obtained in this example are shown in FIG. 7; the graph shows that the scheme disclosed by the invention is higher in stripping and leaching rates when being used for different types of battery pole pieces, and the scheme disclosed by the invention has universality.
Finally, it is also noted that, in the present disclosure, relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
While the disclosure has been disclosed above by the description of specific embodiments thereof, it should be understood that various modifications, improvements or equivalents of the disclosure may be devised by those skilled in the art within the spirit and scope of the appended claims. Such modifications, improvements and equivalents are intended to be included within the scope of the present disclosure as claimed.
Claims (9)
1. A method for recycling waste positive pole pieces of a lithium ion power battery is characterized by comprising the following steps:
s1, cutting the waste positive pole piece of the lithium ion power battery to obtain a cut material;
s2, immersing the cut material obtained in the step S1 into a stripping agent for stripping treatment, and then performing screening treatment under the liquid level to separate oversize products to obtain a liquid-solid mixture; the stripping agent is selected from one or more of citric acid solution, acetic acid solution, phosphoric acid solution, hydrochloric acid solution, sulfuric acid solution, nitric acid solution, glutaric acid solution and perchloric acid solution; the concentration of the stripping agent is 1-10 wt.%; the mass ratio of the stripping agent to the cut material in the stripping treatment is 5-50: 1;
s3, adding a leaching agent into the liquid-solid mixture obtained in the step S2, and performing primary soaking treatment to obtain a first mixed system; the leaching agent is selected from one or more of citric acid solution, acetic acid solution, phosphoric acid solution, hydrochloric acid solution, sulfuric acid solution, nitric acid solution, glutaric acid solution and perchloric acid solution; after the leaching agent is added, the solute concentration of the leaching agent reaches 15-40 wt.%; the addition amount of the leaching agent is determined by the molar ratio of (Ni + Co + Mn +2Li) to H+Calculating according to the ratio of 1: 2-10;
s4, adding a leaching auxiliary agent into the first mixed system obtained in the step S3, and performing second soaking treatment to obtain a second mixed system; the leaching auxiliary agent is one or a mixture of more of hydrogen peroxide, sodium sulfite, sulfur dioxide, hydrogen sulfide, sodium chloride and potassium chloride;
and S5, filtering the second mixed system obtained in the step S4 to obtain a metal salt solution of the positive electrode material and leaching residues, and respectively recovering the metal salt solution and the leaching residues.
2. The method for recycling the waste positive pole piece of the lithium-ion power battery as claimed in claim 1, wherein in step S1, the size of the cut material is 0.5-5 cm.
3. The method for recycling the waste positive pole piece of the lithium-ion power battery according to claim 1 or 2, wherein in the step S2, the stripping process further comprises vibration or stirring treatment; in step S2, the reaction temperature is maintained at 20-80 ℃.
4. The method for recycling the waste positive electrode plate of the lithium-ion power battery according to claim 1 or 2, wherein the step S2 further comprises: a protective agent is also added in the stripping treatment process to inhibit aluminum leaching and/or improve the quality of recovered aluminum; the protective agent comprises an inorganic protective agent and/or an organic protective agent, wherein the inorganic protective agent is a soluble inorganic copper salt; the organic protective agent is one or a mixture of sodium benzoate, melamine and tween 20.
5. The method for recycling the waste positive pole piece of the lithium-ion power battery as claimed in claim 4, wherein the protective agent is soluble inorganic copper salt, and the amount of the soluble inorganic copper salt added is Cu2+Calculated as 200 and 1000 ppm;
or the protective agent is sodium benzoate, and the addition amount of the sodium benzoate is 200-700 ppm;
or the protective agent is melamine, and the addition amount of the melamine is 1-100 ppm;
or the protective agent is Tween 20, and the addition amount of the Tween 20 is 10-100 ppm.
6. The method for recycling the waste positive pole piece of the lithium-ion power battery as claimed in claim 1, wherein the solute concentration of the leaching agent is 20-35wt.% after the leaching agent is added in step S3.
7. The method for recycling the waste positive pole piece of the lithium-ion power battery as claimed in claim 1, wherein in step S3, the time of the first soaking treatment is 10-120min after the leaching agent is added; the reaction temperature was maintained at 20-100 ℃.
8. The method for recycling the waste positive pole piece of the lithium-ion power battery as claimed in claim 1, wherein in step S4, the concentration of the leaching aid is 6-35 wt.%; after the leaching auxiliary agent is added, the time of the second soaking treatment is 30-150 min.
9. The method for recycling the waste positive pole piece of the lithium-ion power battery as claimed in claim 1, wherein in step S4, the leaching auxiliary agent is hydrogen peroxide; cooling the temperature of the first mixed system obtained in the step S3 to below 50 ℃ before adding the hydrogen peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010584131.4A CN111477990B (en) | 2020-06-24 | 2020-06-24 | Method for recycling waste positive pole piece of lithium ion power battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010584131.4A CN111477990B (en) | 2020-06-24 | 2020-06-24 | Method for recycling waste positive pole piece of lithium ion power battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111477990A CN111477990A (en) | 2020-07-31 |
| CN111477990B true CN111477990B (en) | 2020-10-09 |
Family
ID=71763995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010584131.4A Active CN111477990B (en) | 2020-06-24 | 2020-06-24 | Method for recycling waste positive pole piece of lithium ion power battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111477990B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4256641A1 (en) * | 2021-01-06 | 2023-10-11 | Solid Power Operating, Inc. | Method for separation, segregation, and recovery of constituent materials from electrochemical cells |
| CN113502398A (en) * | 2021-07-09 | 2021-10-15 | 郑州中科新兴产业技术研究院 | Method and device for stripping and leaching out anode piece of retired battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108899604A (en) * | 2018-06-28 | 2018-11-27 | 郑州中科新兴产业技术研究院 | Utilize the method for waste lithium cell anode pole piece preparation ternary anode material precursor |
| CN109687051A (en) * | 2018-12-25 | 2019-04-26 | 云南能投汇龙科技股份有限公司 | A kind of method for recycling anode material of waste and old lithium ion battery |
| CN110620277A (en) * | 2019-09-24 | 2019-12-27 | 中国矿业大学 | Method for separating and recovering valuable metal from waste lithium ion battery anode material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10777843B2 (en) * | 2018-10-31 | 2020-09-15 | Nissan North America, Inc. | Regenerated lithium-ion cathode materials having modified surfaces |
-
2020
- 2020-06-24 CN CN202010584131.4A patent/CN111477990B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108899604A (en) * | 2018-06-28 | 2018-11-27 | 郑州中科新兴产业技术研究院 | Utilize the method for waste lithium cell anode pole piece preparation ternary anode material precursor |
| CN109687051A (en) * | 2018-12-25 | 2019-04-26 | 云南能投汇龙科技股份有限公司 | A kind of method for recycling anode material of waste and old lithium ion battery |
| CN110620277A (en) * | 2019-09-24 | 2019-12-27 | 中国矿业大学 | Method for separating and recovering valuable metal from waste lithium ion battery anode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111477990A (en) | 2020-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108470951B (en) | Method for recovering valuable metals in waste nickel-cobalt-manganese ternary lithium ion battery | |
| CN107317064A (en) | A kind of recovery method of waste lithium cell | |
| CA3077604C (en) | Method for separating copper from nickel and cobalt | |
| CN111477990B (en) | Method for recycling waste positive pole piece of lithium ion power battery | |
| EP4103755A1 (en) | A process for recovering metals from recycled rechargeable batteries | |
| EP3950977A1 (en) | A process for recovering cobalt ion, nickel ion and manganese ion from metal-containing residues | |
| CN108384955A (en) | A method of from selectively carrying lithium in waste material containing lithium battery | |
| CN108390120A (en) | A kind of method of lithium in selective recovery waste lithium ion cell anode material | |
| US20210317547A1 (en) | Process for recovering metals from recycled rechargeable batteries | |
| CN108264068B (en) | Method for recovering lithium in lithium-containing battery waste | |
| KR20230156432A (en) | How to recover valuable metals from spent lithium-ion batteries | |
| CN108400403A (en) | A method of preparing lithium carbonate with waste material containing lithium electrode | |
| CN112853120A (en) | LiHCO recovered and leached from waste lithium battery3Method for deeply removing fluorine from solution | |
| CN116632395A (en) | Method for recycling valuable metals in waste batteries | |
| CN114381601A (en) | Method for gradient separation of valuable metals in waste ternary lithium ion battery anode material | |
| EP3006580B1 (en) | Method for producing nickel-containing acidic solution | |
| CN114039119B (en) | Electrolytic stripping of waste lithium iron phosphate battery anode material | |
| TWI625882B (en) | Method for recovering positive electrode material resources in waste lithium iron battery | |
| US8974754B2 (en) | Method for producing nickel-containing acid solution | |
| CN113846225B (en) | Method for combined treatment of coarse hydrogen-producing cobalt oxide and waste ternary anode | |
| CN114606394B (en) | Method for recycling aluminum from waste anode material | |
| WO2024034327A1 (en) | Method of treating waste battery | |
| CN115927851A (en) | Method for recovering lithium from lithium battery | |
| CN116365082A (en) | Method for selectively extracting lithium from waste lithium ion battery black powder and clean and utilization of all components | |
| TW202145632A (en) | Method for recycling valuable metals from waste lithium batteries capable of achieving recycling rate about 99.9% and purity of each element above 98% |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |