CN110615486A - Process for selectively extracting valuable metals from waste power lithium batteries and preparing ternary cathode material - Google Patents
Process for selectively extracting valuable metals from waste power lithium batteries and preparing ternary cathode material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
A process for selectively extracting valuable metals from waste power lithium batteries and preparing a ternary cathode material comprises the following steps; (1) completely discharging, disassembling, ultrasonically stripping, calcining and grinding the recovered waste lithium battery to obtain the required LiNi1/ 3Mn1/3CoO2A positive electrode material; (2) reacting LiNi1/3Mn1/3CoO2The anode material adopts a hydrometallurgy method, so thatLeaching with mild acid and reducing agent, and controlling the ratio of the anode material to the added acid to be 20-60mL/g, so as to further obtain leachate rich in lithium and precipitate containing nickel, cobalt and manganese; (3) leaching the precipitate with trace amount of acid and reducing agent, and controlling the ratio of precipitate to acid to be 20-60mL/g to obtain metal-rich salt solution; (4) and (2) coprecipitating the metal salt solution to obtain a ternary precursor, adding 3-10% of lithium source in excess according to the mass of the precursor, and calcining at a selected temperature to obtain the ternary cathode material with good electrochemical performance. The invention can realize the resource utilization of metal and solve the problem of harmful garbage pollution, and has lower cost.
Description
Technical Field
The invention relates to the technical field of effective recovery of valuable metals of waste batteries, in particular to a process for selectively extracting valuable metals and preparing a ternary positive electrode material from waste power lithium batteries.
Background
With the rapid development of science and technology, lithium ion batteries have the advantages of high energy, relatively long service life and the like, and are widely used in life of people, but the service life is only 2-3 years due to excessive charging and discharging times, so that the waste output is also excessive. The metals contained in the lithium ion battery are all harmful metals, so that the environment ecology is polluted non-negligibly, the manganese, nickel, cobalt and lithium and other metals are effectively recycled at present, the environment pollution can be effectively relieved, the recycling can be realized, the problem of resource shortage is solved, and the waste classification developed in China at present can more effectively promote the recycling of waste batteries.
At present, the treatment technology of waste lithium batteries is a hydrometallurgy technology, metals in a positive electrode material are completely leached out by using high-concentration inorganic acid or organic acid such as hydrochloric acid and sulfuric acid, but the problem of separation of subsequent metals is still complex, the metals cannot be effectively recycled, the cost of the high-concentration acid is high, the economic benefit is poor, and how to treat the high-efficiency recycled metal resources becomes an urgent problem at present.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a process for selectively extracting valuable metals from waste power lithium batteries and preparing a ternary cathode material again, a novel method for effectively realizing short-range coupling selective extraction of Li and repair and regeneration of the cathode material by adopting a method combining leaching and material repair is adopted, the method can realize metal resource utilization and solve the problem of harmful garbage pollution, and the cost is low.
In order to achieve the purpose, the invention adopts the technical scheme that:
a process for selectively extracting valuable metals from waste power lithium batteries and preparing a ternary cathode material comprises the following steps;
(1) completely discharging, disassembling, ultrasonically stripping, calcining and grinding the recovered waste lithium battery to obtain the required LiNi1/3Mn1/3CoO2A positive electrode material;
(2) reacting LiNi1/3Mn1/3CoO2The anode material is leached by a hydrometallurgy method by using mild acid and a reducing agent, the ratio of the anode material to the added acid is controlled to be 20-60mL/g, and further leaching solution rich in lithium and precipitate containing nickel, cobalt and manganese are obtained; drying the obtained precipitate in an oven at 80 ℃ for 10 hours, grinding and storing the precipitate in an agate mortar, recording the volume and storing the supernatant, and facilitating the subsequent ICP test;
(3) leaching the precipitate with trace amount of acid and reducing agent, and controlling the ratio of precipitate to acid to be 20-60mL/g to obtain metal-rich salt solution;
(4) and (2) coprecipitating the metal salt solution to obtain a ternary precursor, adding 3-10% of lithium source in excess according to the mass of the precursor, and calcining at a selected temperature to obtain the ternary cathode material with good electrochemical performance.
The leaching temperature in the step (2) is as follows: leaching time is as follows at 40-90 deg.C: 2-60min, liquid-solid ratio: 20-60mL/g, stirring speed: 200 and 600 rpm.
In the step (2), the concentration of acid in the leaching agent is 0.2-3mol/L, the concentration of the reducing agent is 1-5 vol.%, the selected acid is one of inorganic acid or organic acid, hydrochloric acid, phosphoric acid, oxalic acid, citric acid, ascorbic acid and tartaric acid, and the reducing agent is one of hydrogen peroxide, sodium thiosulfate and ascorbic acid.
The leaching conditions in the step (3) are as follows: leaching temperature: leaching time is as follows at 50-90 deg.C: 10-50min, liquid-solid ratio: 20-60mL/g, 0.05-0.3mol/L of acid concentration, 0-2 vol.% of reducing agent concentration, one of hydrochloric acid, phosphoric acid, sulfuric acid and nitric acid as leaching acid, and one of hydrogen peroxide, sodium persulfate and ascorbic acid as reducing agent.
In the coprecipitation in the step (4), the pH is 7-12, the concentration of a precipitator is 0.5-2mol/L, the temperature is 20-60 ℃, the reaction and aging time is 6-48 h, the precipitator is one of sodium hydroxide, sodium carbonate and oxalic acid, and the ratio of the concentration of a metal salt solution to the concentration of the precipitator is 1: 1.
In the step (4), the calcination temperature in a muffle furnace is 700-1000 ℃, and the time is 10-12 h. .
The invention has the beneficial effects that:
(1) the method has the advantages of simple and feasible operation flow, low temperature, low power, low energy consumption, no generation of other harmful gases, economy and environmental protection;
(2) the step leaching can effectively recover metals, solve the problem that the metals are difficult to separate, save the recovery cost and avoid secondary pollution due to the low-concentration acid.
(3) For transition valuable metals, because of similar chemical properties, it is currently difficult and complicated to separate each metal individually, so that these metals can be sufficiently reused while solving the problem of resource shortage by performing the repair by a simple method.
Drawings
FIG. 1 is a flow chart of selective extraction of Li from waste lithium batteries and regeneration of materials.
Figure 2 is an XRD pattern of a precipitated product and a ternary material obtained by leaching under different conditions with certain acid.
FIG. 3 is an SEM image of a precursor and a ternary material obtained by acid leaching to obtain a precipitated product and regeneration preparation.
FIG. 4 is a graph of LiNi synthesized at different temperatures1/3Mn1/3Co1/3O2The first charge-discharge curve diagram of the anode material.
FIG. 5 is a graph of LiNi synthesized at different temperatures1/3Mn1/3Co1/3O2Positive electrode material multiplying power test chart.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
In the invention, the core steps of separation-re-leaching-regeneration are mainly adopted, firstly, a certain acid with mild low concentration is used for carrying out a single-factor experiment, and the optimal metal separation condition is gradually determined by analyzing the acid concentration, the reaction temperature, the liquid-solid ratio, the reducing agent amount and the leaching time; secondly, a trace amount of certain acid is adopted, factor conditions and kinetic experiments are further optimized, and the fact that metal ions of nickel, cobalt and manganese are reduced to 2-valent metal ions is determined, so that abundant raw materials can be provided for preparing a precursor in the next step; finally, by using a traditional simple coprecipitation method, the proportion of each metal in the metal salt solution is properly adjusted to obtain a precursor with a more excellent structure, and the ternary material with good electrochemical performance is prepared. Compared with other separation and recovery processes, the process has the advantages of mild reaction conditions, low temperature, short time, less acid consumption, high efficiency and high separation efficiency, can recycle valuable metals, and meets the aims of economy, high efficiency and environmental protection of recovery.
In the preferable embodiment of (2) in the present invention, the leaching conditions are: leaching temperature: leaching time is as follows at 40-90 deg.C: 2-60min, liquid-solid ratio: 20-60mL/g, stirring speed: 200 and 600 rpm. The concentration of certain acid in the leaching agent is 0.2-3mol/L, and the concentration of the reducing agent is 1-5 vol.%. In a preferred embodiment, the conditions are: the time is 30-60min, the temperature is 60-90 ℃, the stirring speed is 400rpm, and the acid concentration is 0.4-1.0 mol/L.
In the (3) preferred embodiment of the present invention, the leaching conditions are: leaching temperature: leaching time is as follows at 50-90 deg.C: 10-50min, liquid-solid ratio: 20-60mL/g, acid concentration 0.05-0.25mol/L, reducing agent concentration 0-2 vol.%, preferable scheme, the conditions are: the time is 30-60min, the temperature is 50-80 ℃, and the acid concentration is 0.05-0.2 mol/L.
In a preferred embodiment of (4) of the present invention, the precursor preparation conditions are: the pH is 7-12, the concentration of the precipitator is 0.5-2mol/L, the temperature is 20-60 ℃, the reaction and aging time is 6-48 h, the calcination temperature of the synthetic ternary material is 700-1000 ℃, and the preferable scheme is as follows: the preparation conditions of the precursor are as follows: the pH value is 10-12, the concentration of the precipitator is 1-2mol/L, the temperature is 30-60 ℃, the reaction and aging time is 8-24h, and the muffle furnace calcination temperature is 800-1000 ℃.
All experimental conditions of the single-factor experiment are subjected to 3 parallel experiments, and the average value of the 3 experiments is taken as the final experimental result.
As shown in fig. 2: different leaching conditions result in the XRD pattern of the precipitation and commercial ternary material (leaching conditions: 0.6mol/L acid, 80 ℃, 4 vol.% reducing agent, 20mL/g, 30 min; (2):0.6mol/L acid, 80 ℃, 4 vol.% reducing agent, 40mL/g, 20 min; (3):0.6mol/L acid, 80 ℃, 1 vol.% reducing agent, 40mL/g, 30 min; (4):0.6mol/L acid, 80 ℃, 4 vol.% reducing agent, 40mL/g, 30 min.)
As shown in fig. 3: a, B and C are respectively precipitates obtained by leaching certain acid under the optimal condition, coprecipitating to prepare a precursor, and synthesizing LiNi at the optimal calcination temperature1/3Mn1/3Co1/3O2SEM image of the cathode material.
As shown in fig. 4: synthesis of LiNi at different temperatures1/3Mn1/3Co1/3O2The first charge-discharge curve diagram of the anode material.
As shown in fig. 5: synthesis of LiNi at different temperatures1/3Mn1/3Co1/3O2Positive electrode material multiplying power test chart.
Example 1:
(1) discharging, disassembling, ultrasonically stripping and calcining the waste lithium batteries of different models obtained by recovery to obtain the required positive electrode material (LiNi)1/3Mn1/3CoO2)。
(2) Weighing the required ternary materials, putting the ternary materials into a three-neck flask, controlling the reaction temperature by using a water bath kettle, adding the required acid content and hydrogen peroxide, and starting timing. Adding oxalic acid with the concentration of 0.2mol/L, the temperature of 40 ℃, the time of 20min, 1 vol.% of hydrogen peroxide, the liquid-solid ratio of 20mL/g and the stirring speed of 400rpm to obtain a Li-containing supernatant and a nickel-cobalt-manganese-containing precipitate suspension.
(3) And filtering the obtained turbid liquid by using a vacuum suction filter, repeatedly washing and precipitating for 3 times by using distilled water to respectively obtain a precipitate and a leaching solution, drying the obtained precipitate in an oven at 80 ℃ for 10 hours, grinding and storing the precipitate in an agate mortar, recording the volume and storing the supernatant, and facilitating the subsequent ICP test.
(4) The method for re-leaching the transition metal nickel-cobalt-manganese-rich precipitate obtained under the optimal leaching condition still adopts a single-factor experiment to obtain excellent leaching conditions, and precipitates are found to be dissolved by respectively researching that the concentration of hydrochloric acid is 0.05mol/L, the temperature is 50 ℃, the time is 20min, the concentration of hydrogen peroxide is 2 vol%, and the liquid-solid ratio is 20 mL/g.
(5) And evaporating and concentrating the obtained metal salt solution to obtain the metal salt concentration of 0.5mol/L, and preparing the precursor. By adopting a sodium hydroxide coprecipitation method, the reaction pH, the metal salt concentration/the sodium hydroxide concentration and the reaction temperature are researched, the metal salt concentration and the sodium hydroxide concentration are obtained to be 1:1 according to a chemical reaction equation, the temperature is 40 ℃, the pH is 12, the precipitate is dried to obtain a required precursor, and the performance of the synthetic material is judged according to characterization methods such as XRD, SEM and the like.
(6) Mixing the obtained Ni1/3Co1/3Mn1/3O2The sample is prepared by adding LiOH with the excess of 5% as a lithium source, grinding and mixing uniformly, putting the mixture into a crucible, calcining the mixture in a muffle furnace at 900 ℃ for 12 hours, and researching the optimal conditions of the synthesized sample through SEM, XRD and electrochemical test.
Example 2:
(1) discharging, disassembling, ultrasonically stripping and calcining the waste lithium batteries of different models obtained by recovery to obtain the required positive electrode material (LiNi)1/3Mn1/3CoO2)。
(2) A single-factor experiment is designed for the oxalic acid leaching ternary material, the required ternary material is weighed and placed into a three-neck flask, a water bath is used for controlling the reaction temperature, the required acid content and hydrogen peroxide are added, and timing is started. Wherein the acid concentration is 0.5mol/L, the temperature is 50 ℃, the time is 30min, the hydrogen peroxide is 3 vol.%, and the liquid-solid ratio is 40mL/g, so that a suspension containing Li supernatant and nickel-cobalt-manganese-containing precipitate can be obtained.
(3) And filtering the obtained turbid liquid by using a vacuum suction filter, repeatedly washing and precipitating for 3 times by using distilled water to respectively obtain a precipitate and a leaching solution, drying the obtained precipitate in an oven at 80 ℃ for 10 hours, grinding and storing the precipitate in an agate mortar, recording the volume and storing the supernatant, and facilitating the subsequent ICP test.
(4) The method for re-leaching the transition metal nickel-cobalt-manganese-rich precipitate obtained under the leaching conditions still adopts a single-factor experiment to obtain excellent leaching conditions, the concentration of the added hydrochloric acid is 0.2mol/L, the temperature is 70 ℃, the time is 30min, the concentration of hydrogen peroxide is 1 vol.%, the liquid-solid ratio is 30mL/g, and the precipitate can be dissolved only by adding a trace amount of acid.
(5) And evaporating and concentrating the obtained metal salt solution to obtain the metal salt with the concentration of 1mol/L, and preparing the precursor. By adopting a sodium hydroxide coprecipitation method, the reaction pH, the metal salt concentration/the sodium hydroxide concentration and the reaction temperature are researched, the metal salt concentration and the sodium hydroxide concentration are obtained to be 1:1 according to a chemical reaction equation, the temperature is 50 ℃, the pH is 11, a precursor is obtained by precipitation and drying, and the performance of the synthetic material is judged according to characterization methods such as XRD, SEM and the like.
(6) Mixing the obtained Ni1/3Co1/3Mn1/3O2The sample is prepared by adding 7% of excess LiOH as a lithium source, grinding and mixing uniformly, putting the mixture into a crucible, calcining the mixture in a muffle furnace at 800 ℃ for 12 hours, and researching the best conditions of the synthesized sample through SEM, XRD and electrochemical test.
Example 3:
(1) discharging, disassembling, ultrasonically stripping and calcining the waste lithium batteries of different models obtained by recovery to obtain the required positive electrode material (LiNi)1/3Mn1/3CoO2)。
(2) A single-factor experiment is designed for the oxalic acid leaching ternary material, the required ternary material is weighed and placed into a three-neck flask, a water bath is used for controlling the reaction temperature, the required acid content and hydrogen peroxide are added, and timing is started. Wherein the acid concentration is 1.0mol/L, the temperature is 80 ℃, the time is 60min, the hydrogen peroxide is 5 vol.%, and the liquid-solid ratio is 60mL/g, so that a suspension containing Li supernatant and nickel-cobalt-manganese-containing precipitate can be obtained.
(3) And filtering the obtained turbid liquid by using a vacuum suction filter, repeatedly washing and precipitating for 3 times by using distilled water to respectively obtain a precipitate and a leaching solution, drying the obtained precipitate in an oven at 80 ℃ for 10 hours, grinding and storing the precipitate in an agate mortar, recording the volume and storing the supernatant, and facilitating the subsequent ICP test.
(4) And (3) carrying out re-leaching on the transition metal nickel-cobalt-manganese-rich precipitate obtained under the leaching conditions, still adopting a single-factor experiment to obtain excellent leaching conditions, adding hydrochloric acid with the concentration of 0.2mol/L, the temperature of 80 ℃, the time of 30min, hydrogen peroxide with the concentration of 2 vol.%, and the liquid-solid ratio of 40mL/g, wherein all precipitates are dissolved.
(5) And evaporating and concentrating the obtained metal salt solution to obtain the metal salt with the concentration of 2mol/L, and preparing the precursor. By adopting a sodium hydroxide coprecipitation method, the reaction pH, the metal salt concentration/sodium hydroxide concentration and the reaction temperature are researched, the metal salt concentration and the sodium hydroxide concentration are obtained to be 1:1 according to a chemical reaction equation, the temperature is 60 ℃, the pH is 11, and the performance of the synthetic material is judged according to characterization methods such as XRD, SEM and the like.
(6) Mixing the obtained Ni1/3Co1/3Mn1/3O2The sample is prepared by adding LiOH with the excess of 5% as a lithium source, grinding and mixing uniformly, putting the mixture into a crucible, calcining the mixture in a muffle furnace at 800 ℃ for 12 hours, and researching the optimal conditions of the synthesized sample through SEM, XRD and electrochemical test.
Claims (6)
1. A process for selectively extracting valuable metals from waste power lithium batteries and preparing a ternary cathode material is characterized by comprising the following steps;
(1) completely discharging, disassembling, ultrasonically stripping, calcining and grinding the recovered waste lithium battery to obtain the required LiNi1/3Mn1/3CoO2A positive electrode material;
(2) reacting LiNi1/3Mn1/3CoO2The anode material is leached by a hydrometallurgy method by using mild acid and a reducing agent, the ratio of the anode material to the added acid is controlled to be 20-60mL/g, and further leaching solution rich in lithium and precipitate containing nickel, cobalt and manganese are obtained; drying the obtained precipitate in an oven at 80 deg.C for 10 hr, grinding in agate mortar for preservation, and recording the supernatantThe product is large in volume and stored, so that the subsequent ICP test is facilitated;
(3) leaching the precipitate with trace amount of acid and reducing agent, and controlling the ratio of precipitate to acid to be 20-60mL/g to obtain metal-rich salt solution;
(4) and (2) coprecipitating the metal salt solution to obtain a ternary precursor, adding 3-10% of lithium source in excess according to the mass of the precursor, and calcining at a selected temperature to obtain the ternary cathode material with good electrochemical performance.
2. The process for selectively extracting valuable metals from waste power lithium batteries and preparing the ternary positive electrode material according to claim 1, wherein the leaching temperature in the step (2) is as follows: leaching time is as follows at 40-90 deg.C: 2-60min, liquid-solid ratio: 20-60mL/g, stirring speed: 200 and 600 rpm.
3. The process for selectively extracting valuable metals and preparing the ternary positive electrode material from the waste power lithium batteries according to claim 1, wherein the concentration of the acid in the leaching agent in the step (2) is 0.2-3mol/L, the concentration of the reducing agent is 1-5 vol.%, the selected acid is one of inorganic acid or organic acid, hydrochloric acid, phosphoric acid, oxalic acid, citric acid, ascorbic acid and tartaric acid, and the reducing agent is one of hydrogen peroxide, sodium thiosulfate and ascorbic acid.
4. The process for selectively extracting valuable metals from waste power lithium batteries and preparing the ternary positive electrode material according to claim 1, wherein the leaching conditions in the step (3) are as follows: leaching temperature: leaching time is as follows at 50-90 deg.C: 10-50min, liquid-solid ratio: 20-60mL/g, 0.05-0.3mol/L of acid concentration, 0-2 vol.% of reducing agent concentration, one of hydrochloric acid, phosphoric acid, sulfuric acid and nitric acid as leaching acid, and one of hydrogen peroxide, sodium persulfate and ascorbic acid as reducing agent.
5. The process for selectively extracting valuable metals from waste power lithium batteries and preparing the ternary cathode material according to claim 1, wherein in the coprecipitation in the step (4), the pH is 7-12, the concentration of a precipitator is 0.5-2mol/L, the temperature is 20-60 ℃, the reaction and aging time is 6-48 h, the precipitator is one of sodium hydroxide, sodium carbonate and oxalic acid, and the concentration ratio of a metal salt solution to the precipitator is 1: 1.
6. The process for selectively extracting valuable metals from waste power lithium batteries and preparing the ternary cathode material as claimed in claim 1, wherein the calcination temperature in the muffle furnace in the step (4) is 700 ℃ and 1000 ℃ for 10-12 h.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112117507A (en) * | 2020-11-19 | 2020-12-22 | 中南大学 | Method for efficiently recycling and regenerating waste lithium ion battery anode material |
| CN112142589A (en) * | 2020-09-27 | 2020-12-29 | 厦门理工学院 | Method for synthesizing cobalt oxalate dihydrate from leaching solution of positive active material of waste lithium battery |
| CN112591806A (en) * | 2020-12-15 | 2021-04-02 | 中南大学 | Method for recovering and regenerating anode active material of waste lithium ion battery |
| CN112607789A (en) * | 2020-12-15 | 2021-04-06 | 中南大学 | Process for recovering valuable metals and regenerating anode materials of waste lithium ion batteries |
| CN114875238A (en) * | 2022-05-20 | 2022-08-09 | 北京化工大学 | Method for recycling nickel, manganese, cobalt and lithium in waste lithium battery ternary cathode material |
| US11502345B2 (en) * | 2012-04-04 | 2022-11-15 | Worcester Polytechnic Institute | Method and apparatus for recycling lithium-ion batteries |
| CN115432741A (en) * | 2022-09-23 | 2022-12-06 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Method for recycling waste lithium battery positive plate and battery |
| CN117339913A (en) * | 2023-10-31 | 2024-01-05 | 科立鑫(珠海)新能源有限公司 | Waste battery recovery system |
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| CN112591806A (en) * | 2020-12-15 | 2021-04-02 | 中南大学 | Method for recovering and regenerating anode active material of waste lithium ion battery |
| CN112607789A (en) * | 2020-12-15 | 2021-04-06 | 中南大学 | Process for recovering valuable metals and regenerating anode materials of waste lithium ion batteries |
| CN114875238A (en) * | 2022-05-20 | 2022-08-09 | 北京化工大学 | Method for recycling nickel, manganese, cobalt and lithium in waste lithium battery ternary cathode material |
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Application publication date: 20191227 |