CN108559846B - Method for comprehensively recovering anode material of waste lithium ion battery - Google Patents
Method for comprehensively recovering anode material of waste lithium ion battery Download PDFInfo
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- CN108559846B CN108559846B CN201810156038.6A CN201810156038A CN108559846B CN 108559846 B CN108559846 B CN 108559846B CN 201810156038 A CN201810156038 A CN 201810156038A CN 108559846 B CN108559846 B CN 108559846B
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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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- 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
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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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 method for comprehensively recovering a waste lithium ion battery anode material, and belongs to the technical field of lithium ion battery material recovery. The method comprises the steps of firstly, uniformly mixing a certain amount of carbon-containing solid reducing agents such as coal dust, coke powder and the like and a certain amount of concentrated sulfuric acid with anode material powder obtained by splitting, crushing and screening waste lithium ion batteries, then reacting and curing the mixture for a period of time at the temperature of 100-. The method does not need a roasting and activating process, and has low energy consumption and little environmental pollution; the reagent with wide source and low price is used, and the cost is low; the concentrated sulfuric acid curing reaction condition is adopted, so that the recovery rate of useful elements is high.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery material recovery, and particularly relates to a method for comprehensively recovering useful elements in a waste lithium ion battery anode material.
Background
Lithium ion batteries are widely used in the fields of portable devices, electric vehicles, reserve power supplies, satellites, and the like due to the advantages of high working voltage and specific energy, stable discharge voltage, light weight, small volume, long cycle life, no memory effect, and the like. As the lithium ion battery technology advances, the yield increases, and the amount of waste thereof also increases year by year. The scrapping age of the lithium ion battery is generally 2-3 years, the existing recovery system is not scaled, the recovery rate is low, most of the waste lithium ion batteries are not effectively treated, the environment is polluted, and a large amount of useful resources are wasted. Therefore, the waste lithium battery resource recycling industry is in urgent need of being promoted.
In the method for treating the anode material of the waste lithium ion battery, the recovery process based on the hydrometallurgy is relatively mature, and the application in the industry is relatively wide. The lithium ion battery anode material mainly comprises a lithium cobaltate, a lithium nickelate, a lithium manganate and nickel cobalt manganese ternary anode material and the like, and in order to recover valuable metals such as nickel cobalt manganese and the like, the most widely applied method is to react the anode material with an inorganic acid and leach the valuable metals by taking hydrogen peroxide as a reducing agent. Because chlorine and nitrogen oxides are generated in the process of leaching the cathode material by hydrochloric acid and nitric acid, the problems of safety and pollution exist, so the existing inorganic acid leaching mainly comprises alkaline leaching for removing aluminum-alkaline leaching residue sulfuric acid + H2O2Leaching, purifying, extracting and producing valuable metal salt. CN103035977A discloses a method for recovering valuable metals from waste lithium ion batteries, which mainly adopts brine discharge, manual disassembly, alkaline leaching separation (or low-temperature roasting), reduction acid leaching (sulfuric acid and hydrogen peroxide), chemical precipitation and extraction of valuable metals in anode materials. In the process flow, the core lies in the leaching process of the anode material, the leaching process directly determines the recovery rate of valuable metals, the effect of the process flow also influences the subsequent impurity removal process to a great extent, and the rate influences the rate of the whole process flow. The cost is high because a large amount of hydrogen peroxide is consumed.
CN101519726A discloses a method for recovering valuable metals by roasting waste lithium ion batteries, which is mainly characterized in that lithium cobaltate anode materials are roasted and degummed at 500-850 ℃, then mixed with concentrated sulfuric acid and sulfate for size mixing, and subjected to secondary roasting at 350-600 ℃ in an electric furnace to convert metals such as copper, cobalt and the like into water-soluble sulfate, copper and cobalt are extracted and recovered, and then sodium carbonate is used for precipitating lithium. Although the method obtains higher metal recovery rate, the method has the advantages of high acid consumption, high energy consumption, high cost, low safety and no environmental pollution, and a large amount of toxic gas is generated by roasting. CN107083483A and CN 106921000 a disclose a ball mill mechanical activation leaching method, which shortens the leaching time, improves the metal leaching rate, and reduces the leaching liquid amount. The method also needs to consume a large amount of acid and reducing agent, the leaching ball milling has high requirements on equipment, and the energy consumption and the cost are increased.
Disclosure of Invention
The invention aims to overcome the defects in the existing technology for comprehensively recovering useful elements from the anode material of the waste lithium ion battery, and provides a comprehensive recovery technology for treating the waste anode material based on the mixed curing of a solid reducing agent and concentrated sulfuric acid, and the technology does not need a roasting and activating process, and has low energy consumption and less environmental pollution; the reagent with wide source and low price is used, and the cost is low; the concentrated sulfuric acid curing reaction condition is adopted, so that the recovery rate of useful elements is high. The purpose of the invention is realized by the following technical scheme.
The method for comprehensively recovering the anode material of the waste lithium ion battery is characterized by comprising the following steps of:
(1) the method comprises the steps of mixing the anode material of the waste lithium ion battery, concentrated sulfuric acid and a solid reducing agent in proportion to prepare a mixture, and reacting and curing the mixture to obtain the solid clinker.
(2) Pulping and leaching the solid clinker obtained in the step (1) by using water or dilute acid, and then carrying out solid-liquid separation to obtain a leaching solution.
(3) And (3) further treating the leachate obtained in the step (2) to recover useful elements.
Further, the waste lithium ion battery anode material in the step (1) is an anode powder material obtained by splitting and crushing waste lithium ion batteries, and contains one or more of lithium cobaltate, lithium nickelate, lithium manganate, lithium iron phosphate and ternary anode materials.
Further, the solid reducing agent in the step (1) is one or more of coal powder, coke powder and carbon powder, and preferably the coal powder with the fixed carbon content of not less than 50%.
Further, the curing conditions of the reaction curing in the step (1) are as follows: the curing temperature is 100-350 ℃, the curing time is 0.5-8 h, the preferred curing temperature is 150-300 ℃, and the curing time is 1-4 h.
Further, the slurry leaching conditions in the step (2) are as follows: the leaching temperature is 30-95 ℃, and the leaching time is 10-120 min. The dilute acid is dilute sulfuric acid with the mass concentration less than or equal to 10 percent.
Further, the mass concentration of the concentrated sulfuric acid in the step (1) is more than or equal to 80%.
Further, the proportional mixing in the step (1) means that the ratio of the number of moles of sulfuric acid in the concentrated sulfuric acid to the total number of moles of all metal elements in the positive electrode material is 1:1 to 3:1, and the ratio of the number of moles of total carbon in the solid reducing agent to the total number of moles of all metal elements in the positive electrode material is 1:6 to 2: 1.
In some embodiments, the battery anode material and the solid reducing agent are allowed to contain certain moisture, and the allowable moisture content is limited to the sulfuric acid mass concentration in the mixed material after the mixing is not less than 70%.
In some embodiments, during the slurrying and leaching in the step (2), a proper amount of hydrogen peroxide can be supplemented, and the adding amount of the hydrogen peroxide is 1 to 10 percent of the mass of the anode material of the waste lithium ion battery based on the mass of the hydrogen peroxide.
In some embodiments, the mixture can be heated to 100 ℃ or higher by introducing water vapor into the mixture to initiate the curing reaction, and preferably heated to 120-150 ℃ for initiation.
In some embodiments, the waste lithium ion battery anode material can be pretreated by alkaline solution and then mixed with concentrated sulfuric acid and a solid reducing agent to prepare a mixture. The alkali liquor pretreatment comprises the following steps: stirring and pretreating the waste lithium ion battery anode material and a sodium hydroxide solution with the mass concentration of 5% -30% at 25-100 ℃ for a period of time, filtering to obtain pretreated slag, and mixing the pretreated slag, concentrated sulfuric acid and a solid reducing agent together to prepare a mixture.
According to the method for comprehensively recovering the waste lithium ion battery anode material, the carbon-containing solid reducing agent and concentrated sulfuric acid are directly mixed and then react and are cured, so that the use of reducing agents such as hydrogen peroxide and the like which are expensive and inconvenient to store and transport is avoided or only a small amount of reducing agents is needed to be added, the carbon-containing solid reducing agent is cheap and easy to obtain, and the comprehensive recovery cost is favorably reduced; the curing reaction is carried out in a higher temperature environment, so that the reaction is rapid and complete, the recovery rate of useful elements is high, and the utilization rate of sulfuric acid is high; meanwhile, the reaction heat can be fully utilized during curing, and the energy consumption is reduced.
Drawings
FIG. 1 is a schematic flow diagram of the process of the present invention.
Detailed Description
The invention is further described below with reference to fig. 1.
The invention discloses a method for comprehensively recycling waste lithium ion battery anode materials, which is characterized in that the waste lithium ion battery anode materials after being disassembled and crushed are mixed with concentrated sulfuric acid with the mass concentration of more than or equal to 80% and a solid reducing agent in proportion to prepare a mixture, wherein the ratio of the mole number of sulfuric acid in the concentrated sulfuric acid to the total mole number of all metal elements in the anode materials is 1: 1-3: 1, and the ratio of total carbon in the solid reducing agent to the total mole number of all metal elements in the anode materials is 1: 6-2: 1; the mixture is subjected to reaction curing for a period of time to obtain solid clinker, and the reaction curing conditions are as follows: curing temperature is 100-350 ℃, curing time is 0.5-8 h, preferably curing temperature is 150-300 ℃, and curing time is 1-4 h; then slurrying and leaching the clinker with water or dilute acid, wherein the leaching temperature is 30-95 ℃, and the leaching time is 10-120 min; leaching, filtering to obtain a leaching solution, and recovering useful elements such as lithium, cobalt, nickel, manganese, vanadium and the like from the leaching solution. The anode material is one or a mixture of more of lithium cobaltate, lithium nickelate, lithium manganate, lithium iron phosphate and ternary anode materials. The solid reducing agent is one or more of coal powder, coke powder and carbon powder, and the coal powder with the fixed carbon content of not less than 50 percent is preferred.
In some embodiments, the battery anode material and the solid reducing agent are allowed to contain certain moisture, and the allowable moisture content is limited to the sulfuric acid mass concentration in the mixed material after the mixing is not less than 70%.
In some embodiments, the mixture can be heated to 100 ℃ or higher by introducing water vapor into the mixture to initiate the curing reaction, and preferably heated to 120-150 ℃ for initiation.
In some embodiments, during slurrying and leaching in the step (2), a proper amount of hydrogen peroxide can be supplemented, and the adding amount of the hydrogen peroxide is 1-10% of the mass of the anode material of the waste lithium ion battery based on the mass of the hydrogen peroxide.
In some embodiments, the waste lithium ion battery anode material can be pretreated by alkaline solution and then mixed with concentrated sulfuric acid and a solid reducing agent to prepare a mixture. The pretreatment conditions are as follows: stirring and pretreating the waste lithium ion battery anode material and a sodium hydroxide solution with the mass concentration of 5% -30% at 25-100 ℃ for a period of time, filtering to obtain pretreated slag, and mixing and batching the pretreated slag, concentrated sulfuric acid and a solid reducing agent together.
The process of the present invention is further illustrated by the following non-limiting examples to facilitate the understanding of the contents of the invention and its advantages, but not to limit the scope of the invention, which is defined by the claims.
Example 1
Uniformly mixing 100g of ternary battery positive electrode powder containing 10.63% of cobalt, 6.50% of lithium, 28.30% of nickel, 11.75% of manganese and 3.75% of iron with concentrated sulfuric acid with the mass concentration of 98% and anthracite powder with the fixed carbon content of 75%, wherein the adding amount of the concentrated sulfuric acid is 2:1 of the total molar number of sulfuric acid and all metal elements in the positive electrode material, and the adding amount of the anthracite powder is 1:2 of the total molar number of total carbon in the coal powder and all metal elements in the positive electrode material; the mixture is stirred uniformly and then reacted and cured for 2 hours at 300 ℃, the cured material is obtained and soaked in water for 1 hour at 95 ℃ and the liquid-solid ratio of 5:1mL/g, the solution containing cobalt, nickel, manganese and lithium ions and the leaching residue mainly containing carbon are obtained through solid-liquid separation, the leaching rate of cobalt is 99%, the leaching rate of lithium is 99%, the leaching rate of nickel is 98%, the leaching rate of manganese is 96% and the leaching rate of iron is 8%, and the leaching solution is further purified and separated to recover nickel, cobalt, manganese and lithium.
Example 2
Uniformly mixing 100g of positive electrode powder containing 51.78% of cobalt, 6.14% of lithium and 8.30% of aluminum with 98% of concentrated sulfuric acid and 75% of anthracite powder with fixed carbon content, wherein the adding amount of the concentrated sulfuric acid is 2:1 of the total molar number of sulfuric acid and all metal elements in the positive electrode material, and the adding amount of the anthracite powder is 1:1 of the total molar number of total carbon in the coal powder and all metal elements in the positive electrode material; and (3) uniformly stirring the mixture, reacting and curing for 2 hours at 250 ℃, soaking the obtained cured material in water for 1 hour at 95 ℃ under the condition of a liquid-solid ratio of 8:1mL/g, carrying out solid-liquid separation to obtain a solution containing cobalt, nickel and lithium ions, and further purifying and separating the leachate to recover nickel, cobalt and lithium.
Example 3
Uniformly mixing 100g of ternary battery positive electrode powder containing 4.95% of cobalt, 2.99% of lithium, 12.39% of nickel, 17.01% of manganese, 1.53% of iron and 15% of water with 98% of concentrated sulfuric acid and 85% of coke powder with fixed carbon content, wherein the adding amount of the concentrated sulfuric acid is 2:1 of the total molar ratio of sulfuric acid to all metal elements in the positive electrode material, and the adding amount of the coke powder is 1:1 of the total molar ratio of total carbon in the coke powder to all metal elements in the positive electrode material; stirring the mixture evenly, reacting and curing for 2 hours at 250 ℃, soaking the obtained cured material in water for 1 hour at 95 ℃ and at the liquid-solid ratio of 6:1mL/g, carrying out solid-liquid separation to obtain a solution containing cobalt, nickel, manganese and lithium ions, and further purifying and separating the leachate to recover useful elements.
Example 4
Uniformly mixing 100g of ternary battery positive electrode powder containing 4.95% of cobalt, 2.99% of lithium, 12.39% of nickel, 17.01% of manganese, 1.53% of iron and 15% of water with 98% of concentrated sulfuric acid and 85% of coke powder with fixed carbon content, wherein the adding amount of the concentrated sulfuric acid is 2:1 of the total molar ratio of sulfuric acid to all metal elements in the positive electrode material, and the adding amount of the coke powder is 1:1 of the total molar ratio of total carbon in the coke powder to all metal elements in the positive electrode material; uniformly stirring the mixture, introducing a proper amount of water vapor at 200 ℃ until the temperature of the material is raised to 125 ℃, then carrying out self-heating reaction curing for 4 hours, carrying out water immersion on the cured material for 1 hour at the temperature of 95 ℃ and the liquid-solid ratio of 6:1mL/g by utilizing the self-heating temperature of the reaction to 250 ℃, carrying out solid-liquid separation to obtain a solution containing cobalt, nickel, manganese and lithium ions, and further purifying and separating the leachate to recover useful elements.
Example 5
Taking 100g of ternary battery positive electrode powder containing 5.5% of cobalt, 3.2% of lithium, 12.9% of nickel, 16.1% of manganese, 1.8% of iron and 4.5% of aluminum, stirring and reacting for 1h by using a sodium hydroxide solution with the mass concentration of 10% at the liquid-solid ratio of 3:1mL/g and the temperature of 25-100 ℃, and then filtering; then mixing the filter cake with 98% concentrated sulfuric acid and 88% carbon-containing carbon powder, wherein the concentrated sulfuric acid is added in an amount of 2:1 of the total molar number of the sulfuric acid and all metal elements in the positive electrode material, and the carbon powder is added in an amount of 1:1 of the total molar number of the total carbon in the carbon powder and all metal elements in the positive electrode material; stirring the mixture evenly, reacting and curing for 2 hours at 250 ℃, soaking the obtained cured material in water for 1 hour at 95 ℃ and at the liquid-solid ratio of 6:1mL/g, carrying out solid-liquid separation to obtain a solution containing cobalt, nickel, manganese and lithium ions, and further purifying and separating the leachate to recover useful elements.
Example 6
Uniformly mixing 100g of ternary battery positive electrode powder containing 4.95% of cobalt, 2.99% of lithium, 12.39% of nickel, 17.01% of manganese, 1.53% of iron and 15% of water with 98% of concentrated sulfuric acid and 85% of coke powder with fixed carbon content, wherein the adding amount of the concentrated sulfuric acid is 2:1 of the total molar ratio of sulfuric acid to all metal elements in the positive electrode material, and the adding amount of the coke powder is 1:1 of the total molar ratio of total carbon in the coke powder to all metal elements in the positive electrode material; uniformly stirring the mixture, introducing a proper amount of 200 ℃ water vapor until the temperature of the material rises to 125 ℃, then carrying out self-heating reaction curing for 4 hours, carrying out self-heating reaction at the highest temperature of 250 ℃ to obtain a cured material, leaching the cured material for 1 hour by using 10% dilute sulfuric acid at the temperature of 95 ℃ and the liquid-solid ratio of 6:1mL/g, adding a proper amount of hydrogen peroxide during leaching, wherein the adding amount of the hydrogen peroxide is 2% of the mass of the anode powder according to the weight of hydrogen peroxide, carrying out solid-liquid separation after the leaching is finished to obtain a solution containing cobalt, nickel, manganese and lithium ions, and further purifying and separating the leachate to recover useful elements.
Claims (10)
1. The method for comprehensively recovering the anode material of the waste lithium ion battery is characterized by comprising the following steps of:
(1) preparing a mixture by proportioning a waste lithium ion battery anode material, concentrated sulfuric acid and a solid reducing agent in proportion, and reacting and curing the mixture to obtain solid clinker; the curing conditions of the reaction curing are as follows: curing temperature is 100-350 ℃, and curing time is 0.5-8 h; the waste lithium ion battery anode material is an anode powder material obtained by splitting and crushing waste lithium ion batteries, and contains one or more of lithium cobaltate, lithium nickelate, lithium manganate, lithium iron phosphate and ternary anode materials;
(2) pulping and leaching the solid clinker obtained in the step (1) by using water or dilute acid, and then performing solid-liquid separation to obtain a leaching solution;
(3) and (3) further treating the leachate obtained in the step (2) to recover useful elements, wherein the useful elements are Co, Ni, Li and Mn.
2. The method according to claim 1, wherein the solid reducing agent in step (1) is one or more of coal powder, coke powder and carbon powder.
3. The method according to claim 2, wherein the solid reducing agent in the step (1) is pulverized coal with a fixed carbon content of not less than 50%.
4. The method of claim 1, wherein the aging conditions for the reaction aging of step (1) are: the curing temperature is 150-300 ℃, and the curing time is 1-4 h.
5. The method of claim 1, wherein the slurry leaching conditions of step (2) are: the leaching temperature is 30-95 ℃, the leaching time is 10-120 min, and the dilute acid is dilute sulfuric acid with the mass concentration less than or equal to 10%.
6. The method according to claim 1, characterized in that the mass concentration of the concentrated sulfuric acid in the step (1) is more than or equal to 80%; the proportional mixing means that the ratio of the mole number of sulfuric acid in the concentrated sulfuric acid to the total mole number of all metal elements in the positive electrode material is 1: 1-3: 1, and the ratio of the mole number of total carbon in the solid reducing agent to the total mole number of all metal elements in the positive electrode material is 1: 6-2: 1.
7. The method according to claim 1, wherein the anode material and the solid reducing agent of the waste lithium ion battery in the step (1) are allowed to contain certain moisture, and the allowable moisture content is limited to that the mass concentration of sulfuric acid in the mixed material after blending is not lower than 70%.
8. The method of claim 1, wherein after the mixture is prepared in step (1), steam is introduced into the mixture and the temperature is raised to 120-150 ℃ to initiate the curing reaction.
9. The method according to claim 1, wherein in the step (1), the anode material of the waste lithium ion battery is pretreated by alkali liquor, and then is mixed with concentrated sulfuric acid and a solid reducing agent to prepare a mixture; the alkali liquor pretreatment comprises the following steps: stirring and pretreating the waste lithium ion battery anode material and a sodium hydroxide solution with the mass concentration of 5% -30% at 25-100 ℃ for a period of time, filtering to obtain pretreated slag, and mixing the pretreated slag with concentrated sulfuric acid and a solid reducing agent to prepare a mixture.
10. The method according to claim 1 or 5, characterized in that during slurrying and leaching in the step (2), a proper amount of hydrogen peroxide can be supplemented, and the adding amount of the hydrogen peroxide is 1-10% of the mass of the anode material of the waste lithium ion battery based on the mass of the hydrogen peroxide.
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| CN109599602B (en) * | 2018-11-30 | 2021-07-13 | 成都尤尼瑞克科技有限公司 | Method for resource utilization of waste positive electrode material of lithium battery |
| CN109678144B (en) * | 2019-01-30 | 2020-11-13 | 广东光华科技股份有限公司 | Method for recycling silicon-containing waste graphite of lithium battery |
| CN110835682B (en) * | 2019-09-26 | 2022-07-01 | 北京矿冶科技集团有限公司 | Method for cooperatively treating positive and negative active materials of waste lithium ion battery |
| CN110828926B (en) * | 2019-09-26 | 2022-05-17 | 矿冶科技集团有限公司 | Method for cooperatively recovering metal and graphite from anode and cathode materials of waste lithium ion battery |
| CN111333123A (en) * | 2020-02-14 | 2020-06-26 | 中南大学 | Method for leaching valuable metal from waste lithium ion ternary positive electrode material and preparing ternary positive electrode material precursor |
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| CN114317981A (en) * | 2021-12-31 | 2022-04-12 | 金川镍钴研究设计院有限责任公司 | Purification treatment method of nickel-containing solution |
| CN114480834B (en) * | 2022-01-26 | 2023-04-07 | 江苏大学 | Method and reactor for recovering valuable metals from waste lithium ion batteries |
| CN114525408B (en) * | 2022-02-18 | 2023-06-09 | 中国科学院赣江创新研究院 | Method for combined treatment of waste lithium cobalt oxide anode material and tungsten-containing solid waste |
| CN115287470A (en) * | 2022-08-05 | 2022-11-04 | 中南大学 | Reduction alkaline leaching recovery process for constructing galvanic cell effect |
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| CN103259063A (en) * | 2013-05-13 | 2013-08-21 | 宁夏东方钽业股份有限公司 | Method for recycling transition metal from waste lithium ion battery positive pole material or precursor thereof containing at least one of Mn and Co |
| CN103259063B (en) * | 2013-05-13 | 2016-01-13 | 宁夏东方钽业股份有限公司 | The method of transition metal is reclaimed from the waste and old anode material for lithium-ion batteries containing at least one Co and Mn or its presoma |
| CN105838895A (en) * | 2016-05-16 | 2016-08-10 | 长沙矿冶研究院有限责任公司 | Method for extracting lithium and manganese from lithium-containing manganese-rich slag |
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