CN108232351B - Comprehensive recovery method of waste ternary lithium ion power battery - Google Patents
Comprehensive recovery method of waste ternary lithium ion power battery Download PDFInfo
- Publication number
- CN108232351B CN108232351B CN201810082708.4A CN201810082708A CN108232351B CN 108232351 B CN108232351 B CN 108232351B CN 201810082708 A CN201810082708 A CN 201810082708A CN 108232351 B CN108232351 B CN 108232351B
- Authority
- CN
- China
- Prior art keywords
- solution
- leaching
- lithium ion
- power battery
- ion power
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A comprehensive recovery method of a waste ternary lithium ion power battery comprises the following steps: discharging the waste ternary lithium ion power battery; disassembling, soaking by adopting NaOH solution, carrying out ultrasonic treatment, and carrying out screening, washing, drying and ball milling to obtain a valuable metal reclaimed material; leaching by adopting gluconic acid and hydrochloric acid, and adding hydrogen peroxide as a reducing agent; adding a sodium sulfide solution into the leaching solution, and introducing hydrogen sulfide gas to remove copper; extracting the solution after decoppering to recover Co; recovering Ni from raffinate; recovering Li after distillation. Meanwhile, Cu, Al and graphite are also recovered. The method has the advantages of low cost, simple method and high recovery rate of valuable metals.
Description
Technical Field
The invention relates to a method for recovering waste metals, in particular to a comprehensive recovery method of a waste ternary lithium ion power battery.
Background
The quantity of new energy automobiles kept in China is large, the sales volume of the new energy automobiles increases year by year, and the huge quantity of the new energy automobiles kept is a market with huge opportunity when the automobiles are finally scrapped. The power batteries used in the new energy automobile at present are mainly divided into two types: ternary material lithium ion batteries and lithium iron phosphate lithium ion batteries, wherein the energy density of the ternary material lithium ion batteries is higher. The waste ternary material lithium ion battery contains various valuable metals such as Ni, Co, Li, Cu, Al and the like, and the heavy metals and electrolyte contained in the waste ternary material lithium ion battery can cause great damage to the natural environment. The various valuable metals and non-metallic materials contained in the composite material have great recovery value and space. In the face of huge recovery of waste ternary material lithium ion batteries, China gains some achievements on the recovery technology of the waste ternary material lithium ion batteries, and researches on the recovery technology of the waste ternary material lithium ion batteries enable valuable metals and non-metallic materials in the waste ternary material lithium ion batteries to be effectively utilized, so that resource waste is avoided, and the environment is protected.
Disclosure of Invention
The invention aims to provide a comprehensive recovery method of a waste ternary lithium ion power battery, which has the advantages of low cost, simple method and high recovery rate of valuable metals, and comprises the following steps:
(1) discharging the waste ternary lithium ion power battery to 1.5-2.1V under the constant current condition, standing for 20-60min, continuing to discharge to 0.8-1.2V under the constant current condition, standing for 20-60min, putting the waste ternary lithium ion power battery discharged to 0.8-1.2V into a mixed solution with the NaCl concentration of 1-7mol/L and the KCl concentration of 1-7mol/L, soaking for 1-6h, taking out, and drying for 1-6h at 20-90 ℃ to obtain the completely discharged waste ternary lithium ion power battery;
(2) disassembling the completely discharged waste ternary lithium ion power battery obtained in the step (1), cutting the obtained positive plate into sheets, soaking the positive plate in 10-30L of 0.3-1mol/L NaOH solution at 30-100 ℃ according to the concentration of each kilogram of the positive plate, performing ultrasonic treatment for 0.5-3h, filtering, screening to remove aluminum foil, washing with dilute sulfuric acid and deionized water, drying at the temperature of 100-300 ℃ for 1-5h, and performing ball milling for 1-5h at the temperature of 60-80 ℃ and the vacuum degree of 0.05-0.1MPa to obtain a valuable metal reclaimed material;
(3) leaching the valuable metal reclaimed material obtained in the step (2) by adopting 0.2-3mol/L gluconic acid and 0.2-3mol/L hydrochloric acid, wherein the solid-liquid ratio is 15-35g/L, adding hydrogen peroxide as a reducing agent, the leaching temperature is 50-100 ℃, the leaching time is 1-7h, the stirring speed is 100-;
(4) leaching the leaching residue obtained in the step (3) by using 0.5-3mol/L sulfuric acid solution, adjusting the pH value of the leaching solution obtained by sulfuric acid leaching to 4-6 by using alkali to remove impurities Al and Fe, and then precipitating by using carbonic acid or sodium carbonate to obtain manganese carbonate;
(5) adding 0.5-3mol/L sodium sulfide solution into the leachate obtained in the step (3) for impurity removal, introducing hydrogen sulfide gas according to the amount of 0.1-1L per minute of per liter of leachate while removing impurities to obtain copper sulfide precipitate, and filtering to obtain a solution after copper removal;
(6) adjusting the pH value of the solution obtained in the step (5) after copper removal to 3-5, extracting by using P507 as an extracting agent, wherein the ratio of O/A is 1-3: 1-3, the extraction temperature is 30-50 ℃, the extraction time is 10-120min, standing for 5-20min, back-extracting by using 150-plus 210g/L sulfuric acid solution, the ratio of O/A is 1-3: 1-3, the back-extraction temperature is 30-50 ℃, the back-extraction time is 10-120min, standing for 5-20min, adding saturated oxalic acid solution into the back-extraction solution, stirring for 20-60min at 40-70 ℃, the stirring speed is 100-plus 300r/min, washing the precipitate obtained by solid-liquid separation by deionized water for 1-5 times, drying for 1-10h at 70-90 ℃, then calcining at the temperature of 300-800 ℃ to obtain cobalt oxide;
(7) adjusting the pH value of the raffinate obtained in the step (6) to 2-5, adding 1-3mol/L sulfuric acid solution, heating to 60-90 ℃, adding nickel sulfate seed crystals, cooling to 30-45 ℃ under the vacuum degree of 0.05-0.08MPa, carrying out vacuum filtration, and drying at 80-120 ℃ to obtain nickel sulfate;
(8) distilling and removing impurities from the filtrate obtained in the step (7) through vacuum filtration, and then adding carbonic acid or sodium carbonate into the solution to obtain lithium carbonate;
(9) disassembling the completely discharged waste ternary lithium ion power battery in the step (2) to obtain a negative plate, putting the negative plate into a container, drying at the temperature of 80-120 ℃ for 0.5-2h to separate graphite on the negative plate from copper foil, and recovering the graphite;
(10) paving a charcoal layer with the thickness of 8-12cm at the bottom of a smelting furnace, adding the copper foil obtained in the step (9) into the smelting furnace, heating the smelting furnace to fully melt the copper foil, then slagging off, removing surface slag, then adding a reducing agent to deoxidize, and finally casting to obtain a copper ingot;
(11) melting the aluminum foil sieved and removed in the step (2) at high temperature, adding a mixed flux of cryolite, sodium fluoride, potassium chloride and sodium chloride, stirring at 760 ℃ of 700-.
Further, in the step (1), the concentration of the NaCl solution is 5-6 mol/L;
further, in the step (1), the concentration of the KCl solution is 5-6 mol/L.
Further, in the step (2), the concentration of the NaOH solution was 0.8 mol/L.
Further, in the step (5), 2mol/L sodium sulfide solution is added for impurity removal.
Further, in step (7), the pH of the raffinate was adjusted to 4.
The discharging method of the invention ensures that the waste power battery is discharged completely. Through NaOH soaking, ultrasonic treatment and vacuum ball milling, the activity of the valuable metal reclaimed material is enhanced, the subsequent leaching recovery is facilitated, and the leaching rate is improved. The leaching rate is greatly improved by leaching the gluconic acid and the hydrochloric acid. The extraction of the invention also improves the recovery rate of cobalt and nickel. And the copper is removed by mixing sodium sulfide and hydrogen sulfide, so that the impurity removal efficiency is improved. The invention also recovers Cu, Al, graphite and the like at the same time. By adopting the method, the recovery rates of Co, Ni and Li are respectively over 93 percent, 95.5 percent and 98 percent.
Detailed Description
The present invention is further described with reference to the following examples, which should be construed as limiting the scope of the invention as claimed.
Example 1
A comprehensive recovery method of a waste ternary lithium ion power battery comprises the following steps:
(1) discharging the waste ternary lithium ion power battery to 1.5V under the constant current condition, standing for 20min, continuing to discharge to 0.8V under the constant current condition, standing for 20min, putting the waste ternary lithium ion power battery discharged to 0.8V into a mixed solution with the NaCl concentration of 1mol/L and the KCl concentration of 1mol/L, soaking for 1h, taking out and drying for 1h at 20 ℃ to obtain the completely discharged waste ternary lithium ion power battery;
(2) disassembling the completely discharged waste ternary lithium ion power battery obtained in the step (1), cutting the obtained positive plate into sheets, soaking the positive plate in 10L of 0.3mol/L NaOH solution at 30 ℃, performing ultrasonic treatment for 0.5h, filtering, screening to remove aluminum foil, washing with dilute sulfuric acid and deionized water, drying at 100 ℃ for 1h, and performing ball milling for 1h at 60 ℃ and under the vacuum degree of 0.05MPa to obtain a valuable metal reclaimed material;
(3) leaching the valuable metal reclaimed material obtained in the step (2) by adopting 0.2mol/L gluconic acid and 0.2mol/L hydrochloric acid, wherein the solid-to-liquid ratio is 15g/L, adding hydrogen peroxide as a reducing agent, performing solid-liquid separation at the leaching temperature of 50 ℃ for 1h and the stirring rate of 100r/min to obtain a leaching solution and leaching residues;
(4) leaching the leaching residue obtained in the step (3) by using 0.5mol/L sulfuric acid solution, adjusting the pH value of the leaching solution obtained by sulfuric acid leaching to be 4 by using alkali to remove impurities Al and Fe, and then precipitating by using carbonic acid or sodium carbonate to obtain manganese carbonate;
(5) adding 0.5mol/L sodium sulfide solution into the leachate obtained in the step (3) for impurity removal, introducing hydrogen sulfide gas according to the amount of 0.1L per minute of per liter of leachate while removing impurities to obtain copper sulfide precipitate, and filtering to obtain a solution after copper removal;
(6) adjusting the pH value of the solution subjected to copper removal obtained in the step (5) to 3, extracting by using P507 as an extracting agent, wherein the ratio of O/A to O/A is 1: 3, the extraction temperature is 30 ℃, the extraction time is 10min, standing for 5min, then back-extracting by using 150g/L sulfuric acid solution, the ratio of O/A to O/A is 1: 3, the back-extraction temperature is 30 ℃, the back-extraction time is 10min, standing for 5min, adding saturated oxalic acid solution into the back-extraction solution, stirring for 20min at 40 ℃, the stirring speed is 100r/min, washing the precipitate obtained by solid-liquid separation by deionized water for 1 time, drying for 1h at 70 ℃, and then calcining at 300 ℃ to obtain cobalt oxide;
(7) adjusting the pH value of the raffinate obtained in the step (6) to 2, adding 1mol/L sulfuric acid solution, heating to 60 ℃, adding nickel sulfate seed crystals, cooling to 30 ℃ under the vacuum degree of 0.05MPa, carrying out vacuum filtration, and drying at 80 ℃ to obtain nickel sulfate;
(8) distilling and removing impurities from the filtrate obtained in the step (7) through vacuum filtration, and then adding carbonic acid or sodium carbonate into the solution to obtain lithium carbonate;
(9) disassembling the completely discharged waste ternary lithium ion power battery in the step (2) to obtain a negative plate, putting the negative plate into a container, and drying at 80 ℃ for 0.5h to separate graphite on the negative plate from the copper foil and recover the graphite;
(10) paving a charcoal layer with the thickness of 8cm at the bottom of a smelting furnace, adding the copper foil obtained in the step (9) into the smelting furnace, heating the smelting furnace to fully melt the copper foil, then slagging off, removing surface slag, then adding a reducing agent to deoxidize, and finally casting to obtain a copper ingot;
(11) melting the aluminum foil sieved and removed in the step (2) at high temperature, adding a mixed flux of cryolite, sodium fluoride, potassium chloride and sodium chloride, stirring at 700 ℃, slagging, carrying out alloying treatment, refining and degassing the obtained crude alloy at 700 ℃, and then casting to obtain an aluminum alloy ingot.
Example 2
A comprehensive recovery method of a waste ternary lithium ion power battery comprises the following steps:
(1) discharging the waste ternary lithium ion power battery to 2.1V under the constant current condition, standing for 60min, continuing to discharge to 1.2V under the constant current condition, standing for 60min, putting the waste ternary lithium ion power battery discharged to 1.2V into a mixed solution with the NaCl concentration of 7mol/L and the KCl concentration of 7mol/L, soaking for 6h, taking out and drying for 6h at 90 ℃ to obtain the completely discharged waste ternary lithium ion power battery;
(2) disassembling the completely discharged waste ternary lithium ion power battery obtained in the step (1), cutting the obtained positive plate into sheets, soaking the positive plate in 30L of NaOH solution with the concentration of 1mol/L at 100 ℃, performing ultrasonic treatment for 3 hours, filtering, screening to remove aluminum foil, washing with dilute sulfuric acid and deionized water, drying at the drying temperature of 300 ℃ for 5 hours, and performing ball milling for 5 hours at the vacuum degree of 0.1MPa at 80 ℃ to obtain valuable metal reclaimed materials;
(3) leaching the valuable metal reclaimed material obtained in the step (2) by adopting 3mol/L gluconic acid and 3mol/L hydrochloric acid, wherein the solid-to-liquid ratio is 35g/L, adding hydrogen peroxide as a reducing agent, leaching at 100 ℃, for 7h, stirring at 900r/min, and performing solid-liquid separation to obtain a leaching solution and leaching residues;
(4) leaching the leaching residue obtained in the step (3) by using a 3mol/L sulfuric acid solution, adjusting the pH value of a leaching solution obtained by sulfuric acid leaching to be 6 by using alkali to remove impurities Al and Fe, and precipitating by using carbonic acid or sodium carbonate to obtain manganese carbonate;
(5) adding 3mol/L sodium sulfide solution into the leachate obtained in the step (3) for impurity removal, introducing hydrogen sulfide gas according to the amount of 1L per minute of per liter of leachate while removing impurities to obtain copper sulfide precipitate, and filtering to obtain a solution after copper removal;
(6) adjusting the pH value of the solution subjected to copper removal obtained in the step (5) to 5, extracting by using P507 as an extracting agent, comparing the ratio of O/A to 3: 1, extracting at 50 ℃ for 120min, standing for 20min, back-extracting by using 210g/L sulfuric acid solution, comparing the ratio of O/A to 3: 1, at 50 ℃ for 120min, standing for 20min, adding a saturated oxalic acid solution into the back-extraction solution, stirring at 70 ℃ for 60min at the stirring speed of 300r/min, washing the precipitate obtained by solid-liquid separation by deionized water for 5 times, drying at 90 ℃ for 10h, and calcining at 800 ℃ to obtain cobalt oxide;
(7) adjusting the pH value of the raffinate obtained in the step (6) to 5, adding 3mol/L sulfuric acid solution, heating to 90 ℃, adding nickel sulfate seed crystals, reducing the temperature to 45 ℃ at the vacuum degree of 0.08MPa, carrying out vacuum filtration, and drying at 120 ℃ to obtain nickel sulfate;
(8) distilling and removing impurities from the filtrate obtained in the step (7) through vacuum filtration, and then adding carbonic acid or sodium carbonate into the solution to obtain lithium carbonate;
(9) disassembling the completely discharged waste ternary lithium ion power battery in the step (2) to obtain a negative plate, putting the negative plate into a container, drying at 120 ℃ for 2 hours to separate graphite on the negative plate from the copper foil, and recovering the graphite;
(10) laying a charcoal layer with the thickness of 12cm at the bottom of a smelting furnace, adding the copper foil obtained in the step (9) into the smelting furnace, heating the smelting furnace to fully melt the copper foil, then slagging off, removing surface slag, then adding a reducing agent to deoxidize, and finally casting to obtain a copper ingot;
(11) melting the aluminum foil screened and removed in the step (2) at high temperature, adding a mixed flux of cryolite, sodium fluoride, potassium chloride and sodium chloride, stirring at 760 ℃, slagging, carrying out alloying treatment, refining and degassing the obtained crude alloy at 750 ℃, and then casting to obtain an aluminum alloy ingot.
Example 3
A comprehensive recovery method of a waste ternary lithium ion power battery comprises the following steps:
(1) discharging the waste ternary lithium ion power battery to 1.8V under the constant current condition, standing for 40min, continuing to discharge to 1V under the constant current condition, standing for 40min, putting the waste ternary lithium ion power battery discharged to 1V into a mixed solution with the NaCl concentration of 5mol/L and the KCl concentration of 5mol/L, soaking for 3h, taking out, and drying for 3h at 70 ℃ to obtain a completely discharged waste ternary lithium ion power battery;
(2) disassembling the completely discharged waste ternary lithium ion power battery obtained in the step (1), cutting the obtained positive plate into sheets, soaking the sheets in 20L of 0.5mol/L NaOH solution at 50 ℃ according to each kilogram of the positive plate, performing ultrasonic treatment for 1h, filtering, screening to remove aluminum foil, washing with dilute sulfuric acid and deionized water respectively, drying at 200 ℃ for 2h, and performing ball milling for 2h at 70 ℃ and under the vacuum degree of 0.06MPa to obtain valuable metal reclaimed materials;
(3) leaching the valuable metal reclaimed material obtained in the step (2) by adopting 1mol/L gluconic acid and 1mol/L hydrochloric acid, wherein the solid-to-liquid ratio is 20g/L, adding hydrogen peroxide as a reducing agent, leaching at 60 ℃, for 3h, stirring at 300r/min, and carrying out solid-liquid separation to obtain a leaching solution and leaching residues;
(4) leaching the leaching residue obtained in the step (3) by using 1mol/L sulfuric acid solution, adjusting the pH value of the leaching solution obtained by sulfuric acid leaching to 5 by using alkali to remove impurities Al and Fe, and precipitating by using carbonic acid or sodium carbonate to obtain manganese carbonate;
(5) adding 1mol/L sodium sulfide solution into the leachate obtained in the step (3) for impurity removal, introducing hydrogen sulfide gas according to the amount of 0.3L per minute of per liter of leachate while removing impurities to obtain copper sulfide precipitate, and filtering to obtain a solution after copper removal;
(6) adjusting the pH value of the solution subjected to copper removal obtained in the step (5) to 4, extracting by using P507 as an extracting agent, wherein the ratio of O/A to O/A is 1: 2, the extraction temperature is 40 ℃, the extraction time is 50min, standing for 10min, back-extracting by using 160g/L sulfuric acid solution, the ratio of O/A to O/A is 1: 2, the back-extraction temperature is 40 ℃, the back-extraction time is 50min, standing for 10min, adding saturated oxalic acid solution into the back-extraction solution, stirring at 50 ℃ for 30min, and the stirring rate is 200r/min, washing the precipitate obtained by solid-liquid separation by deionized water for 2 times, drying at 80 ℃ for 30h, and then calcining at 400 ℃ to obtain cobalt oxide;
(7) adjusting the pH value of the raffinate obtained in the step (6) to 3, adding 2mol/L sulfuric acid solution, heating to 70 ℃, adding nickel sulfate seed crystals, cooling to 40 ℃ under the vacuum degree of 0.06MPa, carrying out vacuum filtration, and drying at 90 ℃ to obtain nickel sulfate;
(8) distilling and removing impurities from the filtrate obtained in the step (7) through vacuum filtration, and then adding carbonic acid or sodium carbonate into the solution to obtain lithium carbonate;
(9) disassembling the completely discharged waste ternary lithium ion power battery in the step (2) to obtain a negative plate, putting the negative plate into a container, drying at 90 ℃ for 1h to separate graphite on the negative plate from the copper foil, and recovering the graphite;
(10) paving a 9 cm-thick charcoal layer at the bottom of a smelting furnace, adding the copper foil obtained in the step (9) into the smelting furnace, heating the smelting furnace to fully melt the copper foil, removing slag, removing surface slag, adding a reducing agent to deoxidize, and finally casting to obtain a copper ingot;
(11) melting the aluminum foil screened and removed in the step (2) at high temperature, adding a mixed flux of cryolite, sodium fluoride, potassium chloride and sodium chloride, stirring at 730 ℃, slagging, carrying out alloying treatment, refining and degassing the obtained crude alloy at 730 ℃, and then casting to obtain an aluminum alloy ingot.
Example 4
A comprehensive recovery method of a waste ternary lithium ion power battery comprises the following steps:
(1) discharging the waste ternary lithium ion power battery to 2V under the constant current condition, standing for 50min, continuing to discharge to 0.9V under the constant current condition, standing for 50min, putting the waste ternary lithium ion power battery discharged to 0.9V into a mixed solution with 6mol/L of NaCl and 6mol/L of KCl, soaking for 5h, taking out and drying for 5h at 80 ℃ to obtain a completely discharged waste ternary lithium ion power battery;
(2) disassembling the completely discharged waste ternary lithium ion power battery obtained in the step (1), cutting the obtained positive plate into sheets, soaking the positive plate in 20L of 0.8mol/L NaOH solution at 90 ℃ according to the concentration of each kilogram of the positive plate, performing ultrasonic treatment for 2 hours, filtering, screening to remove aluminum foil, washing with dilute sulfuric acid and deionized water respectively, drying at the drying temperature of 200 ℃ for 4 hours, and performing ball milling for 4 hours at the vacuum degree of 0.09MPa at 70 ℃ to obtain valuable metal reclaimed materials;
(3) leaching the valuable metal reclaimed material obtained in the step (2) by adopting 2mol/L gluconic acid and 2mol/L hydrochloric acid, wherein the solid-to-liquid ratio is 30g/L, adding hydrogen peroxide as a reducing agent, leaching at 90 ℃, for 6h, stirring at 800r/min, and performing solid-liquid separation to obtain a leaching solution and leaching residues;
(4) leaching the leaching residue obtained in the step (3) by using a 2mol/L sulfuric acid solution, adjusting the pH value of a leaching solution obtained by sulfuric acid leaching to 5 by using alkali to remove impurities Al and Fe, and precipitating by using carbonic acid or sodium carbonate to obtain manganese carbonate;
(5) adding 2mol/L sodium sulfide solution into the leachate obtained in the step (3) for impurity removal, introducing hydrogen sulfide gas according to the amount of 0.9L per minute of per liter of leachate while removing impurities to obtain copper sulfide precipitate, and filtering to obtain a solution after copper removal;
(6) adjusting the pH value of the solution subjected to copper removal obtained in the step (5) to 4, extracting by using P507 as an extracting agent, comparing the ratio of O/A to 2: 1, extracting at 40 ℃, extracting for 90min, standing for 10min, back-extracting by using 190g/L sulfuric acid solution, comparing the ratio of O/A to 2: 1, extracting at 40 ℃, extracting for 90min, standing for 10min, adding saturated oxalic acid solution into the back-extraction solution, stirring for 50min at 60 ℃, stirring at the speed of 200r/min, washing the precipitate obtained by solid-liquid separation by deionized water for 4 times, drying for 8h at 80 ℃, and calcining at 700 ℃ to obtain cobalt oxide;
(7) adjusting the pH value of the raffinate obtained in the step (6) to 4, adding 2mol/L sulfuric acid solution, heating to 80 ℃, adding nickel sulfate seed crystals, cooling to 40 ℃ under the vacuum degree of 0.07MPa, carrying out vacuum filtration, and drying at 110 ℃ to obtain nickel sulfate;
(8) distilling and removing impurities from the filtrate obtained in the step (7) through vacuum filtration, and then adding carbonic acid or sodium carbonate into the solution to obtain lithium carbonate;
(9) disassembling the completely discharged waste ternary lithium ion power battery in the step (2) to obtain a negative plate, putting the negative plate into a container, and drying at 110 ℃ for 1.5h to separate graphite on the negative plate from the copper foil and recover the graphite;
(10) paving a charcoal layer with the thickness of 11cm at the bottom of a smelting furnace, adding the copper foil obtained in the step (9) into the smelting furnace, heating the smelting furnace to fully melt the copper foil, then slagging off, removing surface slag, then adding a reducing agent to deoxidize, and finally casting to obtain a copper ingot;
(11) melting the aluminum foil sieved and removed in the step (2) at high temperature, adding a mixed flux of cryolite, sodium fluoride, potassium chloride and sodium chloride, stirring at 750 ℃, slagging, carrying out alloying treatment, refining and degassing the obtained crude alloy at 740 ℃, and then casting to obtain an aluminum alloy ingot.
Claims (1)
1. A comprehensive recovery method of a waste ternary lithium ion power battery is characterized by comprising the following steps:
(1) discharging the waste ternary lithium ion power battery to 1.8V under the constant current condition, standing for 40min, continuing to discharge to 1V under the constant current condition, standing for 40min, putting the waste ternary lithium ion power battery discharged to 1V into a mixed solution with the NaCl concentration of 5mol/L and the KCl concentration of 5mol/L, soaking for 3h, taking out, and drying for 3h at 70 ℃ to obtain a completely discharged waste ternary lithium ion power battery;
(2) disassembling the completely discharged waste ternary lithium ion power battery obtained in the step (1), cutting the obtained positive plate into sheets, soaking the sheets in 20L of 0.5mol/L NaOH solution at 50 ℃ according to each kilogram of the positive plate, performing ultrasonic treatment for 1h, filtering, screening to remove aluminum foil, washing with dilute sulfuric acid and deionized water respectively, drying at 200 ℃ for 2h, and performing ball milling for 2h at 70 ℃ and under the vacuum degree of 0.06MPa to obtain valuable metal reclaimed materials;
(3) leaching the valuable metal reclaimed material obtained in the step (2) by adopting 1mol/L gluconic acid and 1mol/L hydrochloric acid, wherein the solid-to-liquid ratio is 20g/L, adding hydrogen peroxide as a reducing agent, leaching at 60 ℃, for 3h, stirring at 300r/min, and carrying out solid-liquid separation to obtain a leaching solution and leaching residues;
(4) leaching the leaching residue obtained in the step (3) by using 1mol/L sulfuric acid solution, adjusting the pH value of the leaching solution obtained by sulfuric acid leaching to 5 by using alkali to remove impurities Al and Fe, and precipitating by using carbonic acid or sodium carbonate to obtain manganese carbonate;
(5) adding 1mol/L sodium sulfide solution into the leachate obtained in the step (3) for impurity removal, introducing hydrogen sulfide gas according to the amount of 0.3L per minute of per liter of leachate while removing impurities to obtain copper sulfide precipitate, and filtering to obtain a solution after copper removal;
(6) adjusting the pH value of the solution subjected to copper removal obtained in the step (5) to 4, extracting by using P507 as an extracting agent, wherein the ratio of O/A to O/A is 1: 2, the extraction temperature is 40 ℃, the extraction time is 50min, standing for 10min, back-extracting by using 160g/L sulfuric acid solution, the ratio of O/A to O/A is 1: 2, the back-extraction temperature is 40 ℃, the back-extraction time is 50min, standing for 10min, adding saturated oxalic acid solution into the back-extraction solution, stirring at 50 ℃ for 30min, and the stirring rate is 200r/min, washing the precipitate obtained by solid-liquid separation by deionized water for 2 times, drying at 80 ℃ for 30h, and then calcining at 400 ℃ to obtain cobalt oxide;
(7) adjusting the pH value of the raffinate obtained in the step (6) to 3, adding 2mol/L sulfuric acid solution, heating to 70 ℃, adding nickel sulfate seed crystals, cooling to 40 ℃ under the vacuum degree of 0.06MPa, carrying out vacuum filtration, and drying at 90 ℃ to obtain nickel sulfate;
(8) distilling and removing impurities from the filtrate obtained in the step (7) through vacuum filtration, and then adding carbonic acid or sodium carbonate into the solution to obtain lithium carbonate;
(9) disassembling the completely discharged waste ternary lithium ion power battery in the step (2) to obtain a negative plate, putting the negative plate into a container, drying at 90 ℃ for 1h to separate graphite on the negative plate from the copper foil, and recovering the graphite;
(10) paving a 9 cm-thick charcoal layer at the bottom of a smelting furnace, adding the copper foil obtained in the step (9) into the smelting furnace, heating the smelting furnace to fully melt the copper foil, removing slag, removing surface slag, adding a reducing agent to deoxidize, and finally casting to obtain a copper ingot;
(11) melting the aluminum foil screened and removed in the step (2) at high temperature, adding a mixed flux of cryolite, sodium fluoride, potassium chloride and sodium chloride, stirring at 730 ℃, slagging, carrying out alloying treatment, refining and degassing the obtained crude alloy at 730 ℃, and then casting to obtain an aluminum alloy ingot.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810082708.4A CN108232351B (en) | 2018-01-29 | 2018-01-29 | Comprehensive recovery method of waste ternary lithium ion power battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810082708.4A CN108232351B (en) | 2018-01-29 | 2018-01-29 | Comprehensive recovery method of waste ternary lithium ion power battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108232351A CN108232351A (en) | 2018-06-29 |
| CN108232351B true CN108232351B (en) | 2020-06-09 |
Family
ID=62668943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810082708.4A Active CN108232351B (en) | 2018-01-29 | 2018-01-29 | Comprehensive recovery method of waste ternary lithium ion power battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108232351B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109449523B (en) * | 2018-10-31 | 2021-09-10 | 天齐锂业资源循环技术研发(江苏)有限公司 | Comprehensive recovery method for waste lithium ion battery |
| CN109504859B (en) * | 2018-12-29 | 2020-08-04 | 启东市北新无机化工有限公司 | Method for recovering cobalt and nickel from waste lithium ion battery |
| CN110767954B (en) * | 2019-09-16 | 2021-01-22 | 天齐锂业（江苏）有限公司 | Method for carrying out distillation defluorination on lithium ion battery powder by mixed acid and synergistic valuable metal leaching |
| CN115210391A (en) * | 2020-03-02 | 2022-10-18 | 锂电池循环有限公司 | Method for treating multiple waste lithium iron phosphate batteries |
| CN111430831B (en) * | 2020-03-11 | 2022-02-15 | 中南大学 | Method for recovering waste lithium ion battery negative electrode material |
| CN112342398A (en) * | 2020-11-13 | 2021-02-09 | 张连军 | Waste metal recovery processing purification method |
| CN114763585B (en) * | 2021-01-14 | 2024-04-09 | 万华化学集团股份有限公司 | Method for preparing cobalt iso-octoate by using waste Raney cobalt catalyst |
| CN113621819B (en) * | 2021-07-21 | 2022-11-15 | 广东邦普循环科技有限公司 | Method for extracting valuable metals from low-grade nickel matte converter slag |
| CN114427032B (en) * | 2022-01-28 | 2024-07-16 | 重庆大学 | Method for separating valuable metals from leaching solution raw materials by adopting precipitation method |
| CN114875450B (en) * | 2022-05-27 | 2023-11-03 | 湖南世纪垠天新材料有限责任公司 | Comprehensive recovery processing method for ternary power battery material |
| CN115305522A (en) * | 2022-06-20 | 2022-11-08 | 赣州海盛硬质合金有限公司 | Waste hard alloy tungsten resource extraction process and system thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107196006A (en) * | 2017-05-19 | 2017-09-22 | 北京矿冶研究总院 | Recycling method of waste lithium ion battery anode current collector |
| CN107460339A (en) * | 2017-07-13 | 2017-12-12 | 超威电源有限公司 | A kind of method that lead oxide is reclaimed in the lead plaster from waste and old lead acid accumulator |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105591171B (en) * | 2015-12-18 | 2017-12-08 | 浙江天能能源科技股份有限公司 | The recovery method of valuable metal in a kind of waste and old nickel-cobalt-manganese ternary lithium ion battery |
| CN105907989B (en) * | 2016-07-08 | 2017-11-10 | 长沙理工大学 | A kind of method of Call Provision and lithium in material from used Li ion cell |
| CN106505272A (en) * | 2016-12-12 | 2017-03-15 | 江西赣锋锂业股份有限公司 | A kind of processing method of anode material of lithium battery waste material |
| CN107083483A (en) * | 2017-04-18 | 2017-08-22 | 中科过程（北京）科技有限公司 | A kind of method for strengthening waste and old lithium ion battery metal recovery |
| CN107190150A (en) * | 2017-07-14 | 2017-09-22 | 湘潭大学 | One kind reclaims lithium, iron, the method for current collector aluminum foil in positive material of waste lithium iron phosphate |
-
2018
- 2018-01-29 CN CN201810082708.4A patent/CN108232351B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107196006A (en) * | 2017-05-19 | 2017-09-22 | 北京矿冶研究总院 | Recycling method of waste lithium ion battery anode current collector |
| CN107460339A (en) * | 2017-07-13 | 2017-12-12 | 超威电源有限公司 | A kind of method that lead oxide is reclaimed in the lead plaster from waste and old lead acid accumulator |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108232351A (en) | 2018-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108232351B (en) | Comprehensive recovery method of waste ternary lithium ion power battery | |
| CN109234524B (en) | Method and system for comprehensively recovering valuable metals from waste ternary lithium batteries | |
| CN100595970C (en) | Method for selectively removing copper from waste lithium ion battery | |
| CN112646974A (en) | Method for recovering valuable metals from waste ternary lithium battery positive electrode material | |
| CN107267759A (en) | Comprehensive recovery method of lithium ion battery anode material | |
| CN102030375A (en) | Method for preparing lithium cobaltate by directly using failed lithium ion battery | |
| CN107871912A (en) | In a kind of used Li ion cell from recovery in leachate caused by valuable metal iron removaling aluminium method | |
| CN107046154B (en) | Method for enhanced reduction leaching of waste ternary lithium battery | |
| CN103035977A (en) | Method for separating and recovering lithium from waste lithium ion battery | |
| CN108011149B (en) | A method of the Call Provision nickel lithium from discarded power battery | |
| CN106450549B (en) | A method of nickel and/or cobalt in cleaning recycling positive electrode | |
| KR100644902B1 (en) | High-rate recovery of valuable metals such as cobalt and lithium from waste lithium secondary batteries | |
| CN108677014B (en) | A kind of recovery method of waste and old power battery | |
| CN114717422B (en) | Method for recovering valuable metals in retired lithium battery by mechanochemical method | |
| CN113921931B (en) | Method for recycling lithium carbonate from retired lithium ion battery black powder through carbothermic reduction | |
| CN114231744A (en) | Method for recovering lithium, cobalt, nickel and manganese from waste lithium batteries | |
| CN113846219A (en) | Method for extracting lithium from waste lithium batteries | |
| CN116632395A (en) | Method for recycling valuable metals in waste batteries | |
| CN112575203A (en) | Method for recycling lithium in waste power lithium battery | |
| CN114381601A (en) | Method for gradient separation of valuable metals in waste ternary lithium ion battery anode material | |
| CN116676493A (en) | Cooperative recovery method of waste lithium ion battery material and high nickel matte | |
| CN116855764A (en) | Method for recycling valuable metals of waste lithium ion battery anode materials based on molten salt auxiliary agent method | |
| CN114574705B (en) | Method for leaching and separating lithium and valuable metals from waste lithium ion battery | |
| CN112310498A (en) | Method for preparing nickel-cobalt-manganese ternary material precursor by using waste ternary battery | |
| CN112481492A (en) | Method for recovering valuable metals from waste lithium battery lithium cobaltate positive electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |