CN114540640A - Lithium battery recycling method - Google Patents
Lithium battery recycling method Download PDFInfo
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- CN114540640A CN114540640A CN202210210325.7A CN202210210325A CN114540640A CN 114540640 A CN114540640 A CN 114540640A CN 202210210325 A CN202210210325 A CN 202210210325A CN 114540640 A CN114540640 A CN 114540640A
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- 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
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- 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
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- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- 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
- C22B7/001—Dry processes
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- 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
- C22B7/007—Wet processes by acid leaching
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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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- 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 discloses a lithium battery recovery method, which comprises the following steps: step 1: soaking the waste lithium battery in a sodium chloride solution and disassembling; step 2: vibrating and filtering the mixture under ultrasonic low frequency to obtain a lithium-containing cathode material; and step 3: removing impurities by oxidizing and roasting treatment; and 4, step 4: heating and leaching by microwave radiation, and filtering to obtain a lithium-containing filter cake and a lithium-free filter cake; and 5: combining lithium-containing filtrate obtained in the step 4, and removing impurities; step 6: precipitating to obtain carbonate solid, filtering, washing and drying to obtain lithium carbonate; and 7: and (4) preparing the lithium-free filter cake in the step (4), ball-milling and roasting to prepare the anode material. The method has the advantages of simplicity, high lithium recovery efficiency, no secondary pollution, low cost and low requirement on equipment corrosion resistance.
Description
Technical Field
The invention relates to the technical field of lithium battery recovery, in particular to a lithium battery recovery method.
Background
With the gradual shortage of energy and the gradual deterioration of the ecological environment of the earth, the development of human civilization is more and more hindered, and the research, development and utilization of new energy and pollution-free novel energy-saving materials become urgent. With the increasing energy demand and the continuous development of the electronic market and the electric vehicle market, the ternary lithium battery is widely applied to the fields of mobile communication, notebook computers, electric vehicles, electric bicycles and the like due to the advantages of high energy density, environmental protection, long service life, light weight and the like.
The ternary lithium battery is a lithium battery using a ternary cathode material of lithium nickel cobalt manganese or lithium nickel cobalt aluminate, and the cathode materials of the lithium ion battery are various and mainly include ternary materials, lithium iron phosphate, lithium nickelate, lithium cobaltate, lithium manganate and the like. The lithium manganate battery has low energy density and poor storage performance and cycle stability at high temperature; the battery using the lithium iron phosphate as the anode material has long charge-discharge cycle life, but has the defects of low energy density, poor charge-discharge rate characteristic and poor high-low temperature performance, and particularly the capacity and the discharge capacity of the battery can be greatly reduced in a low-temperature environment, so that the lithium iron phosphate battery has met development bottlenecks in technology and application; the ternary material integrates the advantages of lithium nickelate, lithium cobaltate and lithium manganate, under the synergistic effect of the ternary material, the comprehensive performance of the ternary material is superior to that of any single compound, and the ternary lithium battery is gradually superior to lithium manganate and lithium iron phosphate batteries due to high energy density and excellent comprehensive performance and is increasingly accepted by the industry, so that the ternary material becomes a mainstream technical route.
With the wide application of ternary lithium batteries, the usage amount of the ternary lithium batteries is also increased year by year, and the environmental problems caused by the waste ternary lithium batteries have attracted wide attention of countries in the world. In addition to the original constituent substances, other new substances are generated by side reactions in the charging and discharging processes of the waste ternary lithium battery, and if the waste ternary lithium battery is discarded in the environment, various harmful substances in the waste ternary lithium battery enter the environment to cause environmental pollution. The waste ternary lithium ion battery contains a large amount of recyclable metal resources with high economic value, such as nickel, cobalt, manganese, lithium and the like in the anode material of the ternary lithium battery, and if the waste ternary lithium battery can be effectively treated and recycled, the pollution to the environment can be reduced, the waste of resources can be avoided, and the waste is changed into valuable. For example, chinese patent publication No. CN111822140A discloses a method for recovering waste soft-package lithium batteries, which is used for recovering lithium batteries.
In the existing method for recovering metals from waste ternary lithium batteries by using a hydrometallurgy technology or a technology combining a pyrometallurgy and hydrometallurgy, sulfuric acid, hydrochloric acid, nitric acid, citric acid and fluorine-containing organic acid are mostly adopted to dissolve nickel cobalt lithium manganate, waste gases such as acid-containing waste water, acid-containing gas and nitrogen oxides are generated in the recovery process, the requirement on the corrosion resistance of leaching equipment is high, and serious pollution is caused to the atmospheric environment and the water environment.
Disclosure of Invention
The invention aims to solve the technical problems of preventing the lithium battery from recycling pollution and reducing the anticorrosion requirement on equipment.
In order to solve the technical problems, the invention provides the following technical scheme:
a lithium battery recycling method comprises the following steps:
step 1: soaking the waste lithium battery in a sodium chloride solution until no bubbles are generated in the soaking, taking out the waste lithium battery, drying, disassembling the waste lithium battery, and separating the positive plate, the negative plate and the diaphragm;
step 2: placing the separated positive plate into an ultrasonic solution for ultrasonic low-frequency oscillation, separating the positive material from the current collector, and filtering to obtain a positive material containing lithium;
and step 3: carrying out oxidizing roasting treatment on the anode material obtained by filtering in the step 2 to remove impurities;
and 4, step 4: putting the anode material oxidized and roasted in the step 3 into an oxalic acid solution, heating and leaching by microwave radiation under stirring, and putting the filtered residue into an oxalic acid-containing solution until the lithium content in the residue is unchanged to obtain a lithium-containing filter cake and a lithium-free filter cake;
and 5: combining the lithium-containing filtrates in the step 4, adding an alkaline compound, adjusting the pH value to be 4-5.5 to remove impurities, and adjusting the pH value to be 7-9 to remove impurities;
step 6: adding a carbonate solution into the solution with the impurities removed in the step 5 or introducing carbon dioxide, precipitating to obtain a carbonate solid, filtering, washing and drying to obtain lithium carbonate;
and 7: and (4) preparing the lithium-free filter cake in the step (4), ball-milling and roasting to prepare the anode material.
The method is simple, the recovery efficiency of lithium is high, no secondary pollution is generated, the cost is low, and the requirement on corrosion resistance of equipment is low.
Preferably, the ultrasonic solution in the step 2 is a dimethylformamide solution, a dimethylacetamide solution or an N-methylpyrrolidone solution.
Preferably, the ultrasonic frequency of the ultrasonic low-frequency oscillation in the step 2 is 20KHz to 100 KHz.
Preferably, the ultrasonic low-frequency oscillation time in the step 2 is 5-30 min, and the oscillation temperature is 20-80 ℃.
Preferably, the roasting temperature in the step 3 is 600-800 ℃.
Preferably, the concentration of the oxalic acid solution in the step 4 is 45-350 g/L.
Preferably, the stirring manner in the step 4 is mechanical stirring or magnetic stirring.
Preferably, step 4 is heated by microwave radiation through a microwave reactor.
Preferably, the power of the microwave reactor is 100-1000W.
Preferably, the alkaline compound in step 5 is sodium hydroxide.
Compared with the prior art, the invention has the beneficial effects that:
the method is simple to operate, does not generate secondary pollution, is low in cost and has low requirement on equipment corrosion resistance, the reaction efficiency can be greatly improved by adopting microwave radiation heating, the efficiency of the whole recovery process is accelerated, and the recovery efficiency of lithium is high.
Drawings
Fig. 1 is a schematic flow chart according to a first embodiment of the present invention.
Detailed Description
In order to facilitate the understanding of the technical solutions of the present invention for those skilled in the art, the technical solutions of the present invention will be further described with reference to the drawings attached to the specification.
The terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present application, "a plurality" means two or more unless specifically limited otherwise.
Example one
Referring to fig. 1, the embodiment discloses a lithium battery recycling method, which includes the following steps:
step 1: and (2) soaking the waste lithium battery in 15% sodium chloride solution for 2 hours until no bubbles are generated in the soaking, taking out the waste lithium battery, drying, disassembling the waste lithium battery, and separating the positive plate, the negative plate and the diaphragm to obtain the positive plate with the positive material.
Step 2: and (3) carrying out ultrasonic oscillation for 5min in a dimethylformamide solution with the ultrasonic frequency of 50KHz, the ultrasonic power of 110W, the oscillation amplitude of 15mm, the oscillation frequency of 100rpm and the temperature of 50 ℃, completely separating the positive electrode material and the current collector, and filtering to obtain the inactivated positive electrode material.
And 3, step 3: and (3) placing the anode material obtained by filtering in the step (2) into a tubular furnace, introducing air, heating to 720 ℃, roasting for 60min, and carrying out oxidizing roasting treatment to remove impurities.
And 4, step 4: mixing oxalic acid solution, positive electrode material and water in a mass ratio of 5:1:15, placing the mixture in a microwave reactor, mechanically stirring or magnetically stirring, specifically, the concentration of the oxalic acid solution is 45-350 g/L, performing microwave radiation reaction for 10min in the microwave reactor with the power of 710W, cooling, filtering and washing to obtain a lithium-containing filter cake and a lithium-free filter cake, simultaneously detecting the lithium content in the lithium-containing filtrate and the lithium-containing filter cake, wherein the leaching rate of lithium is 80.5%, and detecting the lithium content in the lithium-containing filter cake to be 0.005% after the lithium-containing filter cake returns to be leached twice again.
And 5: and (3) combining the lithium-containing filtrates in the step (4), adding a sodium hydroxide solution to adjust the pH value to be 4.6, filtering, washing and precipitating to remove impurities, adjusting the pH value to be 7, filtering, washing and precipitating to remove impurities.
Step 6: adding carbonate solution or introducing carbon dioxide into the solution with the impurities removed in the step 5. Precipitating to obtain carbonate solid, filtering, washing and drying at 100 ℃ to obtain lithium carbonate.
And 7: and adding the lithium-free filter cake into nickel, cobalt and manganese salts in corresponding proportion, and carrying out ball milling roasting to obtain the active ternary cathode material.
Through the above steps, the recovery rate of lithium was 98.20%.
Compared with the existing method, the method has the advantages of simple operation, no secondary pollution, low cost and low requirement on equipment corrosion resistance, and the reaction efficiency can be greatly improved by adopting microwave radiation heating, so that the efficiency of the whole recovery process is accelerated, and the recovery efficiency of lithium is high.
Example two
The embodiment discloses a lithium battery recovery method, which comprises the following steps:
step 1: and (2) soaking the waste lithium battery in 15% sodium chloride solution for 2 hours until no bubbles are generated in the soaking, taking out the waste lithium battery, drying, disassembling the waste lithium battery, and separating the positive plate, the negative plate and the diaphragm to obtain the positive plate with the positive material.
Step 2: and (3) carrying out ultrasonic oscillation for 10min in an N-methyl pyrrolidone solution with the ultrasonic frequency of 50KHz, the ultrasonic power of 110W, the oscillation amplitude of 15mm, the oscillation frequency of 100rpm and the temperature of 45 ℃, completely separating the positive electrode material and the current collector, and filtering to obtain the inactivated positive electrode material.
And step 3: and (3) placing the anode material obtained by filtering in the step (2) into a tubular furnace, introducing air, heating to 720 ℃, roasting for 60min, and carrying out oxidizing roasting treatment to remove impurities.
And 4, step 4: mixing an oxalic acid solution, a positive electrode material and water in a mass ratio of 3:1:10, placing the mixture in a microwave reactor, mechanically stirring or magnetically stirring, specifically, the concentration of the oxalic acid solution is 45-350 g/L, carrying out microwave radiation reaction for 5min in the microwave reactor with the power of 710W, cooling, filtering and washing to obtain a lithium-containing filter cake and a lithium-free filter cake, simultaneously detecting the content of lithium in the lithium-containing filtrate and the lithium-containing filter cake, wherein the leaching rate of lithium is 84.90%, and detecting the content of lithium in the lithium-containing filter cake as 0.035% after the lithium-containing filter cake returns to be leached twice.
And 5: and (4) combining the lithium-containing filtrates in the step (4), adding a sodium hydroxide solution to adjust the pH value to be 4.6, filtering, washing and precipitating to remove impurities, adjusting the pH value to be 7, filtering, washing and precipitating to remove impurities.
Step 6: adding carbonate solution or introducing carbon dioxide into the solution with the impurities removed in the step 5. Precipitating to obtain carbonate solid, filtering, washing and drying at 100 ℃ to obtain lithium carbonate.
And 7: and adding the lithium-free filter cake into nickel, cobalt and manganese salts in corresponding proportion, and carrying out ball milling roasting to obtain the active ternary cathode material.
Through the above steps, the recovery rate of lithium was 98.85%.
EXAMPLE III
The embodiment discloses a lithium battery recovery method, which comprises the following steps:
step 1: and (2) soaking the waste lithium battery in 20% sodium chloride solution for 2 hours until no bubbles are generated in the soaking, taking out the waste lithium battery, drying, disassembling the waste lithium battery, and separating the positive plate, the negative plate and the diaphragm to obtain the positive plate with the positive material.
Step 2: and (3) completely separating the anode material and the current collector by ultrasonic oscillation for 20min in a dimethylacetamide solution with the ultrasonic frequency of 45KHz, the ultrasonic power of 110W, the oscillation amplitude of 15mm, the oscillation frequency of 100rpm and the temperature of 25 ℃, and filtering to obtain the inactivated anode material.
And 3, step 3: and (3) placing the anode material obtained by filtering in the step (2) into a tubular furnace, introducing air, heating to 720 ℃, roasting for 60min, and carrying out oxidizing roasting treatment to remove impurities.
And 4, step 4: mixing an oxalic acid solution, a positive electrode material and water in a mass ratio of 5:1:15, placing the mixture in a microwave reactor, mechanically stirring or magnetically stirring, specifically, the concentration of the oxalic acid solution is 45-350 g/L, performing microwave radiation reaction for 13min in the microwave reactor with the power of 420W, cooling, filtering and washing to obtain a lithium-containing filter cake and a lithium-free filter cake, detecting the lithium content in the lithium-containing filtrate and the lithium-containing filter cake, wherein the leaching rate of lithium is 87.35%, and detecting the lithium content in the lithium-containing filter cake to be 0.021% after the lithium-containing filter cake returns to be leached twice again.
And 5: and (3) combining the lithium-containing filtrates in the step (4), adding a sodium hydroxide solution to adjust the pH value to be 4.6, filtering, washing and precipitating to remove impurities, adjusting the pH value to be 7, filtering, washing and precipitating to remove impurities.
Step 6: adding carbonate solution or introducing carbon dioxide into the solution with the impurities removed in the step 5. Precipitating to obtain carbonate solid, filtering, washing and drying at 100 ℃ to obtain lithium carbonate.
And 7: and adding the lithium-free filter cake into nickel, cobalt and manganese salts in corresponding proportion, and carrying out ball milling roasting to obtain the active ternary cathode material.
Through the above steps, the recovery rate of lithium was 99.05%.
Example four
The embodiment discloses a lithium battery recovery method, which comprises the following steps:
step 1: and (2) soaking the waste lithium battery in a saturated sodium chloride solution for 1.5 hours until no bubbles are generated in the soaking, taking out the waste lithium battery, drying, disassembling the waste lithium battery, and separating the positive plate, the negative plate and the diaphragm to obtain the positive plate with the positive material.
Step 2: and (3) completely separating the anode material and the current collector by ultrasonic oscillation for 15min in a dimethylformamide solution with the ultrasonic frequency of 45KHz, the ultrasonic power of 110W, the oscillation amplitude of 15mm, the oscillation frequency of 100rpm and the temperature of 25 ℃, and filtering to obtain the inactivated anode material.
And step 3: and (3) placing the anode material obtained by filtering in the step (2) into a tubular furnace, introducing air, heating to 720 ℃, roasting for 60min, and carrying out oxidizing roasting treatment to remove impurities.
And 4, step 4: mixing an oxalic acid solution, a positive electrode material and water in a mass ratio of 3:1:10, placing the mixture in a microwave reactor, mechanically stirring or magnetically stirring, specifically, the concentration of the oxalic acid solution is 45-350 g/L, performing microwave radiation reaction for 4min in the microwave reactor with the power of 420W, cooling, filtering and washing to obtain a lithium-containing filter cake and a lithium-free filter cake, detecting the lithium content in the lithium-containing filtrate and the lithium-containing filter cake, wherein the leaching rate of lithium is 78.28%, and detecting the lithium content in the lithium-containing filter cake after the lithium-containing filter cake returns to be leached twice again and then the lithium content in the lithium-containing filter cake is 0.06%.
And 5: and (3) combining the lithium-containing filtrates in the step (4), adding a sodium hydroxide solution to adjust the pH value to be 4.6, filtering, washing and precipitating to remove impurities, adjusting the pH value to be 7, filtering, washing and precipitating to remove impurities.
Step 6: adding carbonate solution or introducing carbon dioxide into the solution with the impurities removed in the step 5. Precipitating to obtain carbonate solid, filtering, washing and drying at 100 ℃ to obtain lithium carbonate.
And 7: and adding the lithium-free filter cake into nickel, cobalt and manganese salts in corresponding proportion, and carrying out ball milling roasting to obtain the active ternary cathode material.
Through the above steps, the recovery rate of lithium was 97.75%.
EXAMPLE five
The embodiment discloses a lithium battery recovery method, which comprises the following steps:
step 1: and (2) soaking the waste lithium battery in a saturated sodium chloride solution for 1.5 hours until no bubbles are generated in the soaking, taking out the waste lithium battery, drying, disassembling the waste lithium battery, and separating the positive plate, the negative plate and the diaphragm to obtain the positive plate with the positive material.
And 2, step: and (3) completely separating the anode material and the current collector by ultrasonic oscillation for 15min in a dimethylacetamide solution with the ultrasonic frequency of 45KHz, the ultrasonic power of 110W, the oscillation amplitude of 15mm, the oscillation frequency of 100rpm and the temperature of 25 ℃, and filtering to obtain the inactivated anode material.
And step 3: and (3) placing the anode material obtained by filtering in the step (2) into a tubular furnace, introducing air, heating to 720 ℃, roasting for 60min, and carrying out oxidizing roasting treatment to remove impurities.
And 4, step 4: mixing an oxalic acid solution, a positive electrode material and water in a mass ratio of 10:1:30, placing the mixture in a microwave reactor, mechanically stirring or magnetically stirring, specifically, the concentration of the oxalic acid solution is 45-350 g/L, performing microwave radiation reaction for 4min in the microwave reactor with the power of 420W, cooling, filtering and washing to obtain a lithium-containing filter cake and a lithium-free filter cake, detecting the lithium content in the lithium-containing filtrate and the lithium-containing filter cake, wherein the leaching rate of lithium is 84.83%, and detecting the lithium content in the lithium-containing filter cake to be 0.037% after the lithium-containing filter cake returns to be leached twice.
And 5: and (3) combining the lithium-containing filtrates in the step (4), adding a sodium hydroxide solution to adjust the pH value to be 4.6, filtering, washing and precipitating to remove impurities, adjusting the pH value to be 7, filtering, washing and precipitating to remove impurities.
Step 6: adding carbonate solution or introducing carbon dioxide into the solution with the impurities removed in the step 5. Precipitating to obtain carbonate solid, filtering, washing and drying at 100 ℃ to obtain lithium carbonate.
And 7: and adding the lithium-free filter cake into nickel, cobalt and manganese salts in corresponding proportion, and carrying out ball milling roasting to obtain the active ternary cathode material.
Through the above steps, the recovery rate of lithium was 98.68%.
Comparative example 1
In the comparative example, the process method in the prior art is the same as that in the third example, except that the oxalic acid solution is leached and reacted for 2 hours in a conventional heating and stirring mode, the primary leaching rate of the obtained roasted slag is only 58.12%, and the reaction can reach 81.33% after the reaction is continued for 3 hours, which shows that the reaction efficiency can be greatly improved by adopting microwave radiation heating in the leaching process, and the efficiency of the whole recovery process is accelerated.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein, and any reference signs in the claims are not to be construed as limiting the claims.
The above-mentioned embodiments only represent embodiments of the present invention, and the protection scope of the present invention is not limited to the above-mentioned embodiments, and it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the concept of the present invention, and these embodiments are all within the protection scope of the present invention.
Claims (10)
1. A lithium battery recycling method is characterized in that: the method comprises the following steps:
step 1: soaking the waste lithium battery in a sodium chloride solution until no bubbles are generated in the soaking, taking out the waste lithium battery, drying, disassembling the waste lithium battery, and separating the positive plate, the negative plate and the diaphragm;
step 2: placing the separated positive plate into an ultrasonic solution for ultrasonic low-frequency oscillation, separating the positive material from the current collector, and filtering to obtain a positive material containing lithium;
and step 3: carrying out oxidizing roasting treatment on the anode material obtained by filtering in the step 2 to remove impurities;
and 4, step 4: putting the anode material oxidized and roasted in the step 3 into an oxalic acid solution, heating and leaching by microwave radiation under stirring, and putting the filtered residue into an oxalic acid-containing solution until the lithium content in the residue is unchanged to obtain a lithium-containing filter cake and a lithium-free filter cake;
and 5: combining the lithium-containing filtrates in the step 4, adding an alkaline compound, adjusting the pH value to be 4-5.5 to remove impurities, and adjusting the pH value to be 7-9 to remove impurities;
step 6: adding carbonate solution or introducing carbon dioxide into the solution with the impurities removed in the step 5. Precipitating to obtain carbonate solid, filtering, washing and drying to obtain lithium carbonate;
and 7: and (4) preparing the lithium-free filter cake in the step (4), ball-milling and roasting to prepare the anode material.
2. A method of recycling a lithium battery as claimed in claim 1, characterized in that: the ultrasonic solution in the step 2 is a dimethylformamide solution, a dimethylacetamide solution or an N-methylpyrrolidone solution.
3. A method of recycling a lithium battery as claimed in claim 1, characterized in that: and the ultrasonic frequency of the ultrasonic low-frequency oscillation in the step 2 is 20 KHz-100 KHz.
4. A method of recycling a lithium battery as claimed in claim 1, characterized in that: in the step 2, the ultrasonic low-frequency oscillation time is 5-30 min, and the oscillation temperature is 20-80 ℃.
5. A method of recycling a lithium battery as claimed in claim 1, characterized in that: the roasting temperature in the step 3 is 600-800 ℃.
6. A method of recycling a lithium battery as claimed in claim 1, characterized in that: the concentration of the oxalic acid solution in the step 4 is 45-350 g/L.
7. A method of recycling a lithium battery as claimed in claim 1, characterized in that: the stirring mode in the step 4 is mechanical stirring or magnetic stirring.
8. A method of recycling a lithium battery as claimed in claim 1, characterized in that: and 4, heating by microwave radiation through a microwave reactor.
9. A lithium battery recycling method according to claim 8, characterized in that: the power of the microwave reactor is 100-1000W.
10. A method of recycling a lithium battery as claimed in claim 1, characterized in that: the alkaline compound in the step 5 is sodium hydroxide.
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| CN116683082A (en) * | 2023-07-13 | 2023-09-01 | 山东产研绿洲环境产业技术研究院有限公司 | Microwave-assisted pyrogenic process-wet process combined process recovery method for waste lithium batteries |
| CN117361649A (en) * | 2023-10-28 | 2024-01-09 | 吉奥环朋科技(扬州)有限公司 | Method for preparing positive electrode material by using scrapped battery |
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| CN107994288A (en) * | 2017-12-14 | 2018-05-04 | 眉山顺应动力电池材料有限公司 | Valuable metal recovery method in waste and old nickle cobalt lithium manganate ternary cell positive material |
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| CN116683082A (en) * | 2023-07-13 | 2023-09-01 | 山东产研绿洲环境产业技术研究院有限公司 | Microwave-assisted pyrogenic process-wet process combined process recovery method for waste lithium batteries |
| CN116683082B (en) * | 2023-07-13 | 2023-11-14 | 山东产研绿洲环境产业技术研究院有限公司 | Microwave-assisted pyrogenic process-wet process combined process recovery method for waste lithium batteries |
| CN117361649A (en) * | 2023-10-28 | 2024-01-09 | 吉奥环朋科技(扬州)有限公司 | Method for preparing positive electrode material by using scrapped battery |
| CN117361649B (en) * | 2023-10-28 | 2024-04-16 | 吉奥环朋科技(扬州)有限公司 | Method for preparing positive electrode material by using scrapped battery |
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