CN114875240A - Method for treating copper-cobalt alloy of waste lithium battery and application - Google Patents
Method for treating copper-cobalt alloy of waste lithium battery and application Download PDFInfo
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- CN114875240A CN114875240A CN202210355901.7A CN202210355901A CN114875240A CN 114875240 A CN114875240 A CN 114875240A CN 202210355901 A CN202210355901 A CN 202210355901A CN 114875240 A CN114875240 A CN 114875240A
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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
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
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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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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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 belongs to the technical field of battery recovery, and discloses a method for treating copper-cobalt alloy of waste lithium batteries and application thereof, wherein the method comprises the following steps: roasting, acid washing and solid-liquid separation are carried out on the waste lithium battery to obtain copper slag containing nickel and cobalt impurities and nickel and cobalt-containing filtrate; briquetting the copper slag containing nickel and cobalt impurities to prepare an anode in an electrolytic cell, taking a copper sheet as a cathode in the electrolytic cell, and adding an electrolyte for electrolysis; and (3) washing the electrolyzed cathode with water to obtain copper, scattering the electrolyzed anode, adding an oxidant and sulfuric acid, stirring and dissolving to obtain a copper sulfate mixed solution, and carrying out evaporative crystallization on the electrolyzed electrolyte to obtain an acid solution and nickel sulfate and cobalt sulfate crystals. In the process of treating the copper-cobalt alloy, the briquetting is adopted to replace the conventional melting briquetting, and the waste lithium battery module or the monomer is used as an electrolysis power supply, so that the energy is saved and better utilized.
Description
Technical Field
The invention belongs to the technical field of battery recovery, and particularly relates to a method for treating copper-cobalt alloy of waste lithium batteries and application of the copper-cobalt alloy.
Background
Because the lithium battery has the advantages of high energy density, high working voltage, long cycle life, large charge-discharge multiplying power and the like, the lithium battery is widely applied to the fields of new energy automobiles, computers, communication and consumer electronics products and energy storage batteries. At present, along with the replacement of lithium batteries, more and more waste lithium batteries need to be treated, the energy is gradually in short supply, and the lithium batteries contain a large amount of valuable metals, so that the recovery of the valuable metals in the lithium batteries becomes indispensable. The existing pyrogenic process for treating waste lithium batteries has the disadvantages that the recycled battery materials contain a large amount of valuable metals, and the separation and investment cost of the valuable metals in the later period is high, so that the valuable metals are directly accumulated as solid wastes, and the environmental pollution and the resource waste are caused.
At present, when battery materials after high-temperature roasting are treated, part of manufacturers remove impurities by adopting high-temperature melting, so that not only is the energy consumption increased again, but also the cost is increased, and the working environment is extremely dangerous. Therefore, the treatment of the battery material after high-temperature roasting and the recovery of valuable metals thereof become difficult and slow. At present, when waste battery materials are treated by adopting an incineration method, the battery materials on the oversize product of the produced by-product are not effectively treated all the time through high-temperature roasting, crushing and screening, but the main reasons for the effective treatment are that nickel, cobalt and copper are generated into alloy, valuable metals are difficult to separate, and the separation cost is high. Therefore, a method for treating waste lithium battery copper-cobalt alloy is urgently needed, the method can meet the industrial production requirements of environmental friendliness, low energy consumption and high resource recovery, the process is safe, the copper-cobalt alloy can be completely treated, the product does not generate waste residues and waste gases, the investment is low, the return is high, and the industrial production requirements are met.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. The method combines physical and chemical methods, can meet the industrial production requirements of environmental friendliness, low energy consumption and high resource recovery, has safe process, can completely treat the copper-cobalt alloy, produces no waste residue and waste gas, has low investment and high return, and meets the industrial production requirements.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for treating waste lithium battery copper-cobalt alloy comprises the following steps:
(1) roasting, acid washing and solid-liquid separation are carried out on the waste lithium battery to obtain copper slag containing nickel and cobalt impurities and nickel and cobalt-containing filtrate;
(2) briquetting the copper slag containing nickel and cobalt impurities to prepare an anode in an electrolytic cell, taking a copper sheet as a cathode in the electrolytic cell, and adding electrolyte for electrolysis;
(3) and washing the electrolyzed cathode with water to obtain copper, scattering the electrolyzed anode, adding an oxidant and sulfuric acid, stirring and dissolving to obtain a copper sulfate mixed solution, and evaporating and crystallizing the electrolyzed electrolyte to obtain an acid solution, nickel sulfate and cobalt sulfate crystals.
Preferably, in the step (1), the roasting temperature is 500-.
Preferably, in the step (1), before the acid washing, the roasted waste lithium battery is crushed and sieved.
Further preferably, the crushing is a crusher with a screen of 8mm, and the screening is a circular vibrating screen with a screen of 80 meshes.
Preferably, in the step (1), the liquid-solid ratio in the acid washing process is (3-10) mL: 1g of the total weight of the composition.
Preferably, in step (1), the acid used in the acid washing process is sulfuric acid.
Preferably, in the step (1), the acid concentration in the acid washing process is 0.5-2 mol/L.
Preferably, in the step (1), the acid washing time is 1-2 h.
Preferably, in the step (2), the briquetting process is to use a briquetting machine to carry out briquetting, so as to obtain the anode in the electrolytic cell, wherein the length, width, height (cm) of the anode is (8-12) × (2-5) × 2.
Preferably, in the step (2), the power supply used in the electrolysis process is a waste lithium battery module or a single battery which is not discharged, and the liquid leakage and damage are avoided.
Further preferably, the power supply used in the electrolysis process is one of a waste ternary battery and a waste lithium iron phosphate battery.
Further preferably, the voltage of the waste lithium battery module can be controlled to be 2.5-3.6V according to the yield, and the voltage of the single battery is not lower than 2.5V.
Preferably, in the step (2), the copper sheet is pure copper, and the purity of the copper sheet is not lower than 99.9%.
Preferably, in the step (2), the electrolyte is copper sulfate.
Further preferably, the pH of the electrolyte is less than or equal to 1.5.
Preferably, in the step (2), the electrolysis time is 2-4 h.
Preferably, in the step (3), the liquid-solid ratio of the water washing is (1-3) mL: 1g, and the washing time is 0.5-1 h.
Preferably, in the step (3), a vacuum rotary evaporator is adopted for evaporative crystallization, and the rotation speed of the vacuum rotary evaporator is 20-40 r/min; the heating medium of the vacuum rotary evaporator adopts heating oil.
Preferably, in the step (3), the temperature of the evaporative crystallization is 120-150 ℃, and the time of the evaporative crystallization is 2-3 h.
Preferably, in the step (3), the anode is broken up by using a closed crusher.
Preferably, in the step (3), the oxidant is one of hydrogen peroxide and sodium hypochlorite.
Further preferably, the oxidant is hydrogen peroxide.
Preferably, in the step (3), the mass ratio of copper, sulfuric acid and oxidant in the anode is 1: (1-2): (0.5-1).
Preferably, in the step (3), the concentration of the sulfuric acid is 0.5-2 mol/L.
Preferably, in the step (3), the stirring speed is 200-300 r/min.
The invention also provides the application of the method in recovering valuable metals.
The main working principle of the invention is as follows:
and (3) anode reaction:
Cu-2e＝Cu 2+ ；
Ni-2e＝Ni 2+ ；
Co-2e＝Co 2+ ；
H 2 O＝H + +OH - (hydrolysis);
SO 4 2- +2H + ＝H 2 SO 4 ；
and (3) cathode reaction:
Cu 2+ +2e＝Cu。
the processing principle of the invention is as follows:
the invention utilizes a method combining physics and chemistry to treat waste lithium batteries, firstly the waste lithium batteries are roasted at high temperature, crushed and screened to obtain secondary battery materials, and valuable metals which are easy to recover in the materials are removed by adding acid washing.
Putting the copper slag after acid washing into a briquetting machine for briquetting to enhance the conductivity among materials, adding a conductive binder or other binders which are easy to remove at the later stage in the process, and using the briquetted copper slag as an anode; taking high-purity pure copper as a negative electrode; adding copper sulfate mixed solution as electrolyte, and taking the battery module or monomer as an electrolysis power supply. In the electrolytic process, copper ions in the solution are separated out at the cathode, passivation can occur due to the high impurity content of the anode copper block, but the nickel-cobalt impurity content in the copper block can be rapidly separated out to enter the solution under the electrolytic action, so that the aim of recovering and separating valuable metals is fulfilled. Because the impurities in the anode copper block are not completely separated after electrolysis and cannot be directly sold, the copper block is scattered by using a crusher, dilute sulfuric acid and hydrogen peroxide are added to dissolve copper to generate a copper sulfate mixed solution which is used as an electrolyte, copper ions generate electrolytic copper under the electrolysis action, and impurity nickel cobalt enters the solution for subsequent treatment.
Adhering nickel-cobalt solution in the electrolytic copper, removing valuable metal solution by washing with water, and selling the solution after reaching the standard; the electrolyzed solution contains a large amount of nickel sulfate, cobalt sulfate and dilute sulfuric acid solution, the dilute sulfuric acid solution is recovered by evaporative crystallization, the nickel sulfate and the cobalt sulfate can directly enter a rear-end leaching process to be used as raw materials, and the recovered dilute sulfuric acid solution can enter a front-end acid washing process and a copper melting process for recycling.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the process of treating the copper slag containing nickel and cobalt impurities, the briquetting is adopted to replace the conventional melting briquetting, and the waste lithium battery module or the single body is used as an electrolytic power supply, so that the energy is saved, the energy is better utilized, and the waste lithium battery adopts resistance discharge at present, thereby directly wasting the energy. The conventional iron powder replacement process is replaced by using electric desorption copper, so that copper can be completely separated out, and impurity doping and energy loss are reduced. The electrolysis process is a self-heating process due to acid output, so that the reaction is accelerated, heating and additional acid addition are not needed to keep the acid amount, and the energy loss is reduced. The nickel cobalt is leached by electrolysis instead of acid leaching, so that the leaching rate is greatly improved. The whole process has no pollution, waste residue and waste gas emission, meets the process requirements of the existing industry on environmental friendliness, low cost, low energy consumption and high resource utilization, and is suitable for future industrial production.
Drawings
FIG. 1 is a process flow diagram of example 1 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The method for treating the copper-cobalt alloy of the waste lithium battery comprises the following steps:
(1) roasting the single waste lithium battery at the temperature of 600 ℃, crushing for 2min by using a crusher, then screening by using a 80-mesh screen, and taking the oversize battery material;
(2) taking 200g of oversize battery material, adding 1L of 1.0mol/L sulfuric acid, stirring for 30min at the stirring speed of 250r/min, then carrying out acid pickling for 1h, and filtering to obtain copper slag containing nickel and cobalt impurities and nickel and cobalt-containing filtrate;
(3) washing copper slag containing nickel and cobalt impurities with water, putting the copper slag into a briquetting machine for briquetting to prepare an anode in an electrolytic cell, taking a workshop waste lithium battery module or a waste lithium battery monomer as an electrolytic power supply, adding a copper sulfate mixed solution as an electrolyte, wherein the copper content is about 20g/L, taking a pure copper sheet as a cathode, and carrying out electrolysis for 2 hours, wherein the process solution is changed from blue to deep red along with heat release and the temperature is about 47 ℃;
(4) after the electrolysis is finished, taking out the electrolytic copper separated out from the cathode after the electrolysis, washing with water (the liquid-solid ratio is 1: 1), and after the inspection is qualified, reaching the national standard and being capable of being directly sold;
(5) taking out the electrolyzed anode, weighing 142g, putting into a crusher for crushing, adding 160g of concentrated sulfuric acid (with the concentration of 98%) and 70g of hydrogen peroxide after crushing, and preparing 1500mL of copper sulfate mixed solution to be used as the electrolyte in the step (3).
(6) Pouring the electrolyzed solution into a vacuum rotary evaporator for evaporation crystallization, wherein the vacuum degree is 0.01MPa, the rotating speed is 30r/min, the heating temperature is 120 ℃, the drying is carried out for 1h, the evaporated solution enters the step (2) and the step (5) for acid preparation, and the crystallized material is naturally air-dried and cooled to obtain the crystal containing nickel sulfate and cobalt sulfate.
FIG. 1 is a process flow diagram of example 1 of the present invention.
Element content detection results:
ICP (inductively coupled plasma spectrometry) was used to measure the content of key elements in the material prepared in example 1 of the present invention, and the results are shown in table 1 below.
TABLE 1
The measured data of the substance content of the crystals are as follows:
TABLE 2
(Cu) recovery rate (mass of electrolytic copper + copper content in electrolytic copper + volume of nickel-cobalt containing filtrate + copper concentration in nickel-cobalt containing filtrate)/mass of cell material + copper content in cell material 100%;
(Ni) recovery (nickel-cobalt containing filtrate volume + nickel content in nickel-cobalt containing filtrate mass + nickel content in crystals 58.7/154.7)/battery charge mass + nickel content of battery charge 100%;
(Co) recovery (volume of nickel-cobalt containing filtrate + cobalt content in crystals + mass of cobalt in nickel-cobalt containing filtrate + mass of cobalt in crystals + mass of nickel in battery charge + 100% mass of nickel in battery charge).
The electrolytic copper obtained by the treatment of the embodiment 1 can be directly sold, the acid pickling leaching solution enters a leaching process to recover valuable metals, the solution is evaporated and crystallized after electrolysis, crystals can enter the leaching process to prepare finished products, the evaporated solution is used for preparing acid and is recycled, and a power supply of an electrolytic cell uses waste lithium battery modules or monomers, so that the energy waste is reduced. The whole process meets the process requirements of the existing industry on environmental friendliness, low cost, low energy consumption and high resource utilization.
Example 2
The method for treating the copper-cobalt alloy of the waste lithium battery comprises the following steps:
(1) roasting the single waste lithium battery at the temperature of 700 ℃, crushing for 2min by using a crusher, screening by using a 80-mesh screen, and taking the oversize battery material;
(2) taking 150g of oversize battery material, adding 1L of 1.5mol/L sulfuric acid, stirring for 30min at the stirring speed of 200r/min, pickling for 1h, and filtering to obtain copper slag containing nickel and cobalt impurities and nickel and cobalt-containing filtrate;
(3) washing copper slag containing nickel and cobalt impurities with water, putting the copper slag into a briquetting machine for briquetting to prepare an anode in an electrolytic cell, taking a workshop waste lithium battery module or a waste lithium battery monomer as an electrolytic power supply, adding a copper sulfate mixed solution as an electrolyte, wherein the copper content is about 23g/L, taking a pure copper sheet as a cathode, and carrying out electrolysis for 2 hours, wherein the process solution is changed from blue to deep red along with heat release and the temperature is about 50 ℃;
(4) after the electrolysis is finished, taking out the electrolytic copper separated out from the cathode after the electrolysis, washing with water (the liquid-solid ratio is 1: 1), and after the inspection is qualified, reaching the national standard and being capable of being directly sold;
(5) taking out the electrolyzed anode copper block, weighing 116g, putting into a crusher for crushing, adding 160g of 98% concentrated sulfuric acid and 70g of hydrogen peroxide after crushing, and preparing into 1500mL of copper sulfate mixed solution for use as the electrolyte in the step (3).
(6) Pouring the electrolyzed solution into a vacuum rotary evaporator for evaporation crystallization, wherein the vacuum degree is 0.01MPa, the rotation speed is 30r/min, the heating temperature is 120 ℃, the drying is carried out for 1h, the evaporated solution enters the step (2) and the step (5) for acid preparation, and the crystallized material is naturally air-dried and cooled to obtain the crystal containing nickel sulfate and cobalt sulfate.
Element content detection results:
ICP (inductively coupled plasma spectrometry) was used to measure the content of key elements in the material prepared in example 2 of the present invention, and the results are shown in table 3 below.
TABLE 3
The measured data of the crystal content are as follows:
TABLE 4
The electrolytic copper obtained by the treatment of the embodiment 2 can be directly sold, the acid pickling leaching solution enters a leaching process to recover valuable metals, the solution is evaporated and crystallized after electrolysis, crystals can enter the leaching process to prepare finished products, the evaporated solution is used for preparing acid and is recycled, and a power supply of an electrolytic cell uses waste lithium battery modules or monomers, so that the energy waste is reduced. The whole process meets the process requirements of the existing industry on environmental friendliness, low cost, low energy consumption and high resource utilization.
Example 3
The method for treating the copper-cobalt alloy of the waste lithium battery comprises the following steps:
(1) roasting the single waste lithium battery at the temperature of 600 ℃, crushing for 3min by using a crusher, then screening by using a 80-mesh screen, and taking the oversize battery material;
(2) taking 250g of oversize battery material, adding 2.0mol/L sulfuric acid, stirring for 30min at the stirring speed of 200r/min, then carrying out acid washing for 1h, and filtering to obtain copper slag containing nickel and cobalt impurities and nickel and cobalt-containing filtrate;
(3) washing copper slag containing nickel and cobalt impurities with water, putting the copper slag into a briquetting machine for briquetting to prepare an anode in an electrolytic cell, taking a workshop waste lithium battery module or a waste lithium battery monomer as an electrolytic power supply, adding a copper sulfate mixed solution as an electrolyte, wherein the copper content is about 25g/L, taking a pure copper sheet as a cathode, and carrying out electrolysis for 2 hours, wherein the process solution is changed from blue to deep red along with heat release and the temperature is about 52 ℃;
(4) after the electrolysis is finished, taking out the electrolytic copper separated out from the cathode after the electrolysis, washing with water (the liquid-solid ratio is 1: 1), and after the inspection is qualified, reaching the national standard and being capable of being directly sold;
(5) and (3) taking out the electrolyzed anode copper block, weighing 186g, putting the anode copper block into a crusher for crushing, adding 200g of concentrated sulfuric acid with the mass fraction of 98% and 90g of hydrogen peroxide after crushing, and preparing 2000mL of copper sulfate mixed solution to be used as the electrolyte in the step (3).
(6) And (3) pouring the electrolyzed solution into a vacuum rotary evaporator for evaporation crystallization, wherein the vacuum degree is 0.01MPa, the rotating speed is 40r/min, the heating temperature is 150 ℃, the drying is carried out for 1h, the evaporated solution enters the step (2) and the step (5) for acid preparation, and the crystallized material is naturally air-dried and cooled to obtain the crystal containing nickel sulfate and cobalt sulfate.
Element content detection results:
ICP (inductively coupled plasma spectrometry) was used to measure the content of key elements in the material prepared in example 3 of the present invention, and the results are shown in table 5 below.
TABLE 5
The measured data of the crystal content are as follows:
TABLE 6
The electrolytic copper obtained by the treatment of the embodiment 3 can be directly sold, the acid pickling leaching solution enters a leaching process to recover valuable metals, the solution is evaporated and crystallized after electrolysis, crystals can enter the leaching process to prepare finished products, the evaporated solution is used for preparing acid and is recycled, and a power supply of an electrolytic cell uses waste lithium battery modules or monomers, so that the energy waste is reduced. The whole process meets the process requirements of the existing industry on environmental friendliness, low cost, low energy consumption and high resource utilization.
Comparative example 1 (step (3) in comparison with example 1, no energization electrolysis was performed)
The method for treating the copper-cobalt alloy of the waste lithium battery in the comparative example comprises the following steps:
(1) roasting the single waste lithium battery at the temperature of 600 ℃, crushing for 2min by using a crusher, then screening by using a 80-mesh screen, and taking the oversize battery material;
(2) taking 200g of oversize battery material, adding 1L of 1.0mol/L sulfuric acid, stirring for 30min at the stirring speed of 250r/min, then carrying out acid pickling for 1h, and filtering to obtain copper slag containing nickel and cobalt impurities and nickel and cobalt-containing filtrate;
(3) washing copper slag containing nickel and cobalt impurities with water, putting the copper slag into a briquetting machine for briquetting, putting the copper slag into an electrolytic bath, adding a copper sulfate mixed solution as an electrolyte, wherein the copper content is about 20g/L, and standing for reaction for 2 hours to obtain a copper block and the electrolyte.
Element content detection results:
ICP (inductively coupled plasma spectrometry) was used to determine the content of key elements in the material prepared in comparative example 1 of the present invention, and the results are shown in table 7 below.
TABLE 7
The measured data of the crystal content are as follows:
TABLE 8
Compared with the comparative example 1, the leaching of nickel and cobalt in the copper block can be accelerated by the electrifying electrolysis in the example 1, and copper ions in the solution are converted into copper to be separated out, so that impurity doping is reduced, and the post-treatment is facilitated. Comparative example 1 since the electrolysis was not performed, nickel and cobalt in the copper ingot were very slowly leached into the electrolyte, and thus the recovery rate of nickel and cobalt was low, and copper ions in the electrolyte could not be converted into copper to be precipitated, and the recovery rate of copper was also lowered.
The present invention is not limited to the above-described embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A method for treating waste lithium battery copper-cobalt alloy is characterized by comprising the following steps:
(1) roasting, acid washing and solid-liquid separation are carried out on the waste lithium battery to obtain copper slag containing nickel and cobalt impurities and nickel and cobalt-containing filtrate;
(2) briquetting the copper slag containing nickel and cobalt impurities to prepare an anode in an electrolytic cell, taking a copper sheet as a cathode in the electrolytic cell, and adding electrolyte for electrolysis;
(3) and washing the electrolyzed cathode with water to obtain copper, scattering the electrolyzed anode, adding an oxidant and sulfuric acid, stirring and dissolving to obtain a copper sulfate mixed solution, and evaporating and crystallizing the electrolyzed electrolyte to obtain an acid solution, nickel sulfate and cobalt sulfate crystals.
2. The method as claimed in claim 1, wherein the temperature of the calcination in step (1) is 500-1000 ℃.
3. The method of claim 1, wherein in step (2), the briquetting is performed by a briquetting machine to obtain anodes in the electrolytic cell, and the anodes have a length, width, and height (cm) of (8-12) × (2-5) × 2.
4. The method according to claim 1, wherein in the step (2), the electrolyte is copper sulfate.
5. The method according to claim 1, wherein in the step (2), the electrolysis time is 2-4 h.
6. The method according to claim 1, wherein in the step (3), the liquid-solid ratio of the water washing is (1-3) mL: 1g, and the washing time is 0.5-1 h.
7. The method according to claim 1, wherein in the step (3), the oxidant is one of hydrogen peroxide and sodium hypochlorite.
8. The method according to claim 1, wherein in the step (3), the mass ratio of the copper, the sulfuric acid and the oxidant in the anode after electrolysis is 1: (1-2): (0.5-1).
9. The method according to claim 1, wherein in the step (3), the concentration of the sulfuric acid is 0.5 to 2 mol/L.
10. Use of the method of any one of claims 1 to 9 for the recovery of metal values.
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| PCT/CN2023/074949 WO2023193517A1 (en) | 2022-04-06 | 2023-02-08 | Method for treating copper-cobalt alloy of waste lithium battery and use thereof |
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| WO2023193517A1 (en) * | 2022-04-06 | 2023-10-12 | 湖南邦普循环科技有限公司 | Method for treating copper-cobalt alloy of waste lithium battery and use thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111373062A (en) * | 2017-11-24 | 2020-07-03 | 住友金属矿山株式会社 | Method for treating waste lithium ion battery |
| CN114204152A (en) * | 2021-12-16 | 2022-03-18 | 恩施市致纯电子材料有限公司 | Recovery process of waste ternary lithium ion battery anode material |
Family Cites Families (5)
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| JP4865745B2 (en) * | 2008-02-13 | 2012-02-01 | Ｊｘ日鉱日石金属株式会社 | Method for recovering valuable metals from lithium batteries containing Co, Ni, Mn |
| AU2012261548B2 (en) * | 2008-11-17 | 2013-02-21 | Rockwood Lithium Inc. | Recovery of lithium from aqueous solutions |
| TWI726033B (en) * | 2016-01-08 | 2021-05-01 | 印度商艾特羅回收股份有限公司 | Process for recovering metal values from spent lithium ion batteries with high manganese content |
| CN113802002B (en) * | 2021-08-17 | 2022-11-15 | 广东邦普循环科技有限公司 | Method for recovering valuable metals in lithium battery by wet process |
| CN114875240A (en) * | 2022-04-06 | 2022-08-09 | 湖南邦普循环科技有限公司 | Method for treating copper-cobalt alloy of waste lithium battery and application |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111373062A (en) * | 2017-11-24 | 2020-07-03 | 住友金属矿山株式会社 | Method for treating waste lithium ion battery |
| CN114204152A (en) * | 2021-12-16 | 2022-03-18 | 恩施市致纯电子材料有限公司 | Recovery process of waste ternary lithium ion battery anode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023193517A1 (en) * | 2022-04-06 | 2023-10-12 | 湖南邦普循环科技有限公司 | Method for treating copper-cobalt alloy of waste lithium battery and use thereof |
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| WO2023193517A1 (en) | 2023-10-12 |
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