CN114583309A - Method for preparing precursor by recycling waste ternary lithium ion battery - Google Patents
Method for preparing precursor by recycling waste ternary lithium ion battery Download PDFInfo
- Publication number
- CN114583309A CN114583309A CN202210219092.7A CN202210219092A CN114583309A CN 114583309 A CN114583309 A CN 114583309A CN 202210219092 A CN202210219092 A CN 202210219092A CN 114583309 A CN114583309 A CN 114583309A
- Authority
- CN
- China
- Prior art keywords
- alkali
- precursor
- lithium ion
- cobalt
- nickel
- 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.)
- Pending
Links
Images
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
-
- 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 relates to the technical field of lithium ion battery recovery, and discloses a method for recovering a precursor prepared from a waste ternary lithium ion battery. The invention has the following advantages and effects: the raw materials used in the method are common and easy to obtain, the process is simple, the requirement on equipment is low, and the method is suitable for large-scale production; the prepared mixed salt has low impurity content, does not need extraction treatment, can be directly used for synthesizing a precursor, and has low cost; the battery has high recovery efficiency, less discharge and environmental protection.
Description
Technical Field
The invention relates to the technical field of lithium ion battery recovery, in particular to a method for preparing a precursor by recovering a waste ternary lithium ion battery.
Background
The lithium ion battery has the advantages of high energy density, small volume, long service life, high safety, little environmental pollution, no memory effect and the like. Since the commercialization of lithium ion batteries, lithium ion batteries have gradually replaced conventional lead acid batteries through 30 years of development.
As one of the important branches of lithium ion batteries, various performances such as energy density, cycle life, cost and the like are comprehensively considered, and the ternary lithium ion battery has outstanding advantages and is favored and widely applied to the fields of 3C, new energy vehicles, energy storage and the like. Particularly in the field of new energy automobiles, in recent years, new energy automobiles are in a well-spraying development stage under the influence of the trouble of environmental pollution and the shortage of fossil energy, and the demand of ternary lithium ion batteries is continuously increased.
The increase in the demand of the ternary battery brings about the following two problems: (1) the method has the advantages that the resources are short, on one hand, the storage amount of partial raw materials for manufacturing the ternary battery in the earth crust is low and uneven, the problem of resource shortage is more severe due to the increase of demand, and on the other hand, due to the influence of international political relations, the resource supply of the upstream raw materials is short, the price is increased, and the price of materials related to lithium batteries is frequently innovative; (2) the method has the advantages that the environment is polluted, the average service life of the ternary lithium power battery is 3-5 years, scrapping treatment is needed when the life cycle is exceeded, if the treatment is not proper, heavy metals such as fluoride, nickel, cobalt, manganese and the like in the battery cause serious pollution, and great pressure is caused on the environment.
The Li in the waste lithium ion battery is recycled and utilized, so that the problem of resource shortage is solved, and the pressure of environmental pollution is relieved.
Disclosure of Invention
The invention aims to provide a method for preparing a precursor by recycling a waste ternary lithium ion battery, which has the advantages of common and easily-obtained raw materials, simple process, low requirement on equipment and suitability for large-scale production; the prepared mixed salt has low impurity content, does not need extraction treatment, can be directly used for synthesizing a precursor, and has low cost; the battery has high recovery efficiency, less discharge and environmental protection.
The technical purpose of the invention is realized by the following technical scheme: a method for preparing a precursor by recycling a waste ternary lithium ion battery comprises the following steps,
s1, discharging, crushing, drying and sorting the ternary lithium ion battery to obtain black powder;
s2, soaking the black powder in alkali, and performing filter pressing to obtain aluminum-removed black powder and a filtrate 1;
s4, leaching to remove nickel, cobalt and manganese in the aluminum black powder by using acid and a reducing agent, and performing filter pressing to obtain a carbon material and a filtrate 2;
s5, adding iron powder into the filtrate 2, and performing filter pressing to obtain copper and a filtrate 3;
s6, adding an oxidant into the filtrate 3, adding alkali to adjust the pH value, precipitating ferric hydroxide, and performing filter pressing to obtain ferric hydroxide and a filtrate 4;
s7, adjusting the pH value of the filtrate 4 by using alkali, precipitating nickel, cobalt and manganese, and obtaining nickel, cobalt and manganese oxide and a filtrate 5 after filter pressing and water washing;
s8, reversely dissolving the nickel-cobalt-manganese hydroxide to prepare a nickel-cobalt-manganese mixed salt solution;
and S9, preparing salt, and carrying out coprecipitation to synthesize a precursor.
The invention is further provided with: in S9, the precursor is a ternary or quaternary precursor, and the chemical general formula of the precursor is as follows: niaCobMncAl1-a-b-c(OH)2Wherein a is more than or equal to 0.3 and less than or equal to 0.96, b is more than 0 and less than or equal to 0.2, c is more than 0 and less than or equal to 0.3, and the tap density of the precursor is 1.6-2.4g/cm3D50 is 3-10 μm.
The invention is further provided with: in S9, the salt concentration of the synthetic precursor is 0.18-0.23mol/L, the alkali is one or two of sodium hydroxide and potassium hydroxide, the alkali concentration is 4-11mol/L, the ammonia water concentration is 10-15mol/L, n (alkali): n (salt) ═ 2.0-2.1, n (ammonia): n (salt) ═ 1-2.
The invention is further provided with: s1, the waste battery is soaked in salt solution for discharging, the salt is one or more of sodium chloride, sodium sulfate, potassium chloride and potassium sulfate, the waste battery is dried after discharging, the drying temperature is 180-230 ℃, the drying time is 1-6h, the sorting comprises airflow sorting and gravity sorting, the content of nickel cobalt lithium manganate in the copper foil after sorting is less than 0.5%, the content of nickel cobalt lithium manganate in the aluminum foil is less than 1%, the content of copper in the black powder is less than 2%, and the content of aluminum is less than 4%. .
The invention is further provided with: including S3, adding acid into the filtrate 1 to obtain aluminum hydroxide precipitate, washing and filter-pressing the precipitate, adding liquid alkali to recover aluminum and preparing sodium metaaluminate.
The invention is further provided with: comprising S10, adding sodium carbonate into the filtrate 5 to precipitate lithium, washing with water, filtering, and recrystallizing to obtain high-purity lithium carbonate.
The invention is further provided with: in S2, the black powder is soaked in alkali to remove aluminum, the alkali is one or two of sodium hydroxide and potassium hydroxide, the concentration of the alkali is 0.1-10mol/L, the solid-to-liquid ratio of the alkali leaching is 1:2-1: 10, n (alkali) n (aluminum) is 1-3, the temperature of the alkali leaching is 60-100 ℃, and the leaching time is 3-8 hours.
The invention is further provided with: in S3, sulfuric acid is used for adjusting pH to precipitate aluminum, wherein the concentration of the sulfuric acid is 1-4mol/L, the pH value of aluminum hydroxide precipitate is 4-6, the reaction time is 3-5h, the aluminum hydroxide is washed with water for removing impurities, the solid-to-liquid ratio of the washing is 1:1-1:5, the washing is carried out for 2-5 times, the washing temperature is 30-60 ℃, 5-10mol/L sodium hydroxide is added into the aluminum hydroxide, the pH value of the solution is controlled to be more than 11, the reaction time is 3-5h, the reaction temperature is 60-80 ℃, and sodium metaaluminate solution is obtained by filtering.
The invention is further provided with: in S4, leaching nickel, cobalt and manganese in the black powder by using acid and a reducing agent, wherein the leaching temperature is 60-90 ℃, the leaching time is 6-12h, the acid is one or more of sulfuric acid, hydrochloric acid and nitric acid, and the reducing agent is one or two of hydrogen peroxide and sodium metabisulfite.
The invention is further provided with: in S5, removing copper by adopting iron powder, wherein the adding amount of the iron powder is 1.1-1.5 times of the mass of copper, the reaction temperature is 80-90 ℃, and the reaction time is 1-2 h; in S6, the oxidant is one or two of hydrogen peroxide or ozone, the alkali is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and ammonia water, the pH of the iron and aluminum removal is 3.8-4.5, the reaction temperature is 80-90 ℃, and the reaction time is 3-5 hours; in S7, the alkali is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and ammonia water, the pH value of the nickel-cobalt-manganese precipitate is 7-9.5, the solid-to-liquid ratio of water washing is 1:2-1:5, the water washing time is 1-2h, and the water washing temperature is 30-70 ℃.
The invention is further provided with: in S8, concentrated sulfuric acid and hydrogen peroxide are used for reversely dissolving nickel-cobalt-manganese precipitate, wherein m (nickel-cobalt-manganese precipitate): m (concentrated sulfuric acid): m (27% hydrogen peroxide) is 1:1-1.1:0.6-0.7, the solid-to-liquid ratio is 1:2-1:4, and the pH value of the obtained salt solution is 3-4.
The invention is further provided with: in S10, lithium-containing wastewater is firstly concentrated, the concentration of lithium after concentration is 15-20g/L, the pH value of the solution is adjusted to be more than 13, the reaction temperature is controlled to be 80-100 ℃, then sodium carbonate is added for precipitating lithium, the molar weight of the sodium carbonate is 1-3 times of that of the lithium, and lithium carbonate is obtained through filtration, water washing and recrystallization.
The invention has the beneficial effects that:
(1) the invention not only can recycle nickel, cobalt, manganese and lithium in the waste ternary batteries, but also can recycle battery shells, aluminum foils and copper foils, and part of impurities such as aluminum and copper in black powder can be recycled in the form of byproducts, so that the recycling efficiency is high, the emission is less and the environmental pollution is less.
(2) The black powder is leached and subjected to multi-stage impurity removal to obtain a high-purity mixed salt solution, and the high-purity mixed salt solution can be directly used for synthesizing a precursor without extraction and purification with high cost, so that the recovery cost can be greatly reduced, and the benefit is improved.
(3) According to the method, aluminum is preliminarily removed through alkaline leaching before acid leaching, so that on one hand, aluminum can be recycled to prepare sodium metaaluminate to be used as a raw material for synthesizing an aluminum-containing precursor; on the other hand, the reduction of the aluminum content is beneficial to reducing the loss of nickel and cobalt in the process of removing iron and aluminum by purification.
(4) The method has the advantages of simple process, mild reaction conditions and low equipment requirement.
(5) The invention is a wet process, does not relate to a roasting reduction process with high energy consumption, and has low cost.
(6) Compared with the prior art of preferentially extracting lithium, the method preferentially recovers nickel, cobalt and manganese and finally recovers lithium.
(7) The method removes calcium and magnesium by precipitating nickel, cobalt and manganese, which is different from the prior art of removing calcium and magnesium by alkaline leaching.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic diagram of the process route of the present invention.
FIG. 2 is an SEM photograph of the quaternary precursor of NCMA (90:5:4:1) prepared in example 4.
FIG. 3 is an SEM photograph of the ternary precursor of NCM (8:1:1) prepared in example 5.
FIG. 4 is an SEM photograph of the ternary precursor of NCM (5:2:3) prepared in example 6.
FIG. 5 is an SEM photograph of ternary precursors of NCM (5:2:3) prepared in example 7.
Detailed Description
The technical solution of the present invention will be clearly and completely described with reference to the specific embodiments. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
Example 1
A nickel-cobalt-manganese mixed salt solution prepared by recycling waste lithium ion batteries is prepared by the following steps:
(1) soaking the waste ternary lithium ion battery in 10 wt% sodium chloride solution for discharging, drying at the drying temperature of 200 ℃ for 5h after discharging, and then performing air flow sorting and gravity sorting to obtain black powder;
(2) adding pure water into the black powder prepared in the step (1) according to the solid-liquid ratio of 1:5 for pulping, adding sodium hydroxide according to the ratio of n (alkali) to n (aluminum) to 1.5, heating to 80 ℃, reacting for 5 hours, carrying out solid-liquid separation after the reaction is finished, and carrying out filter pressing to obtain the aluminum-removed black powder and the filtrate 1.
(3) Adding pure water into the aluminum-removed black powder according to the solid-to-liquid ratio of 1:3 for washing for 2 times, then adding concentrated sulfuric acid, slowly dropwise adding hydrogen peroxide, controlling the reaction temperature to be 85 ℃, reacting for 6 hours, controlling the pH to be more than 3 after the reaction is finished, then carrying out solid-liquid separation, and carrying out filter pressing to obtain a carbon material and a filtrate 2.
(4) Detecting the copper content in the filtrate 2, wherein the copper content is measured according to the following formula (n) (Fe): iron powder was added at a ratio of n (cu) to 1.2, the reaction temperature was controlled at 80 ℃, the reaction was carried out for 1 hour, and copper was recovered by filtration to obtain a filtrate 3.
(5) And (3) slowly adding hydrogen peroxide into the filtrate 3, then adjusting the pH to 4.5 by using 1mol/L sodium hydroxide solution, controlling the reaction temperature to be 85 ℃, reacting for 3 hours, and filtering to obtain iron hydroxide and a filtrate 4.
(6) Adding 10mol/L sodium hydroxide solution into the filtrate 4 to adjust the pH value of the filtrate 4 to 9.5, then filtering to obtain precipitate and filtrate 5, adding pure water into the precipitate according to the solid-to-liquid ratio of 1:3, washing for 3 times, washing for 1h each time with water at the temperature of 50 ℃, removing Li, Ca and Mg in the nickel, cobalt and manganese to obtain nickel, cobalt and manganese oxide precipitate.
(7) Adding pure water into the nickel-cobalt-manganese oxide precipitate according to the proportion of 1:4 for pulping, and then, according to the proportion of m (nickel-cobalt-manganese precipitate): m (concentrated sulfuric acid): and (3) adding concentrated sulfuric acid and hydrogen peroxide in a ratio of m (27% hydrogen peroxide) to 1:1.07:0.6 to prepare a nickel-cobalt-manganese mixed salt solution.
(8) Table 1 shows the components of the black powder prepared according to the present invention, and table 2 shows the contents of nickel, cobalt, manganese and impurities in the mixed salt solution prepared according to the present invention.
TABLE 1 Black powder ingredients
TABLE 2 Nickel cobalt manganese and impurities content in the mixed salt solution
Example 2
A sodium metaaluminate solution prepared by recycling waste lithium ion batteries is prepared by the following steps:
(1) and collecting the filtrate 1 of the alkali-dipped black powder in the example 1, filtering again, adding 1mol/L sulfuric acid, adjusting the pH value of the solution to 5, stirring and aging for 3h, and filtering to obtain aluminum hydroxide precipitate.
(2) Adding pure water with the temperature of 50 ℃ into the aluminum hydroxide precipitate according to the solid-to-liquid ratio of 1:2, and washing for 3 times.
(3) Adding 5mol/L sodium hydroxide into the aluminum hydroxide precipitate, controlling the pH value of the solution to be more than 11, reacting at 60 ℃ for 3h, and filtering to obtain a sodium metaaluminate solution.
(4) The recovery rate of aluminum can reach 85%, the concentration of aluminum in the sodium metaaluminate solution is 40.5g/L, the pH value of the solution is more than 11, and the contents of impurities such as Ni, Co, Mn, Mg, Fe, Cu, Ca and the like in the solution are all less than 10 Mg/L.
Example 3
A lithium carbonate prepared by recycling waste lithium ion batteries is prepared by the following steps:
(1) collecting the lithium-containing wastewater (namely filtrate 5) after nickel, cobalt and manganese are precipitated in the example 1, evaporating and concentrating the lithium-containing wastewater until the lithium content is 18g/L, adjusting the pH value of the solution to be more than 13, and controlling the reaction temperature to be 95 ℃.
(2) Sodium carbonate was added in the ratio of n (Na2CO3) to n (li) 1:1 to obtain lithium carbonate crystals, which were filtered and rinsed 3 times with hot water at 95 ℃.
(3) And dissolving the crystal by using cold water, filtering, evaporating, recrystallizing and drying to obtain a lithium carbonate finished product.
(4) The invention has a lithium recovery rate of more than 80 percent and a lithium content of more than 99.0 percent
Example 4
The NCMA (90:5:4:1) quaternary precursor prepared by the invention is prepared by the following steps:
(1) taking the nickel-cobalt-manganese mixed salt solution prepared in the example 1, supplementing nickel sulfate, cobalt sulfate and manganese sulfate crystals into the mixed salt solution, and preparing the nickel-cobalt-manganese in the solution according to the following proportion: n (Ni) n (Co): n (mn) 90:5:4, and pure water was added to dilute the salt solution to 2 mol/L.
(2) The sodium metaaluminate solution prepared in example 2 was diluted with pure water to 0.2 mol/L.
(3) Simultaneously adding 4mol/L of sodium hydroxide solution with the ammonia water concentration of 10.5mol/L into the reaction kettle, mixing the salt solution and the sodium metaaluminate solution, and controlling n (alkali): n (salt) ═ 2.03:1, n (ammonia): n (salt) ═ 1.4, and the flow ratio of the mixed salt solution to the sodium metaaluminate solution is 10: 1.
(4) The synthesized NCMA quaternary precursor has D50 of 6 +/-0.5 microns and tap density of 2.04g/cm3The content of S is less than or equal to 0.15%, the content of sodium is less than or equal to 0.01%, the content of Ca, Mg, Fe, Cu, Pd, Cd, Zn, Cr and K is less than or equal to 0.001%, and an SEM picture of a precursor is shown in figure 2.
Example 5
The NCM (8:1:1) ternary precursor prepared by the invention has the following preparation process:
(1) taking the nickel-cobalt-manganese mixed salt solution prepared in the example 1, supplementing nickel sulfate, cobalt sulfate and manganese sulfate crystals into the mixed salt solution, and preparing the nickel-cobalt-manganese in the solution according to the following proportion: n (Ni) n (Co): n (mn) ═ 8:1:1, and pure water was added to dilute the salt solution to 2 mol/L.
(2) Simultaneously adding 4mol/L of sodium hydroxide solution into the reaction kettle, wherein the concentration of ammonia water is 10.5mol/L of ammonia water, mixing salt solution, and controlling n (alkali): n (salt) ═ 2.02:1, n (ammonia): n (salt) ═ 1.3.
(3) The NCM811 ternary precursor synthesized by the invention has the D50 of 3.5 +/-0.5 mu m and the tap density of 1.68g/cm3The content of S is less than or equal to 0.15%, the content of sodium is less than or equal to 0.01%, the content of Ca, Mg, Fe, Cu, Pd, Cd, Zn, Cr and K is less than or equal to 0.0015%, and an SEM picture of a precursor is shown in FIG. 3.
Example 6
The preparation method of the NCM (5:2:3) ternary precursor provided by the invention comprises the following steps:
(1) taking the nickel-cobalt-manganese mixed salt solution prepared in the example 1, supplementing nickel sulfate, cobalt sulfate and manganese sulfate crystals into the mixed salt solution, and preparing the nickel-cobalt-manganese in the solution according to the following proportion: n (Ni) n (Co): n (mn) 5:2:3, and pure water was added to dilute the salt solution to 2 mol/L.
(2) Simultaneously adding 4mol/L of sodium hydroxide solution into the reaction kettle, wherein the concentration of ammonia water is 10.5mol/L of ammonia water, mixing salt solution, and controlling n (alkali): n (salt) ═ 2.01:1, n (ammonia): n (salt) ═ 1.2, and the flow ratio of the mixed salt solution to the sodium metaaluminate solution is 10: 1.
(4) The NCM523 ternary precursor synthesized by the invention has the advantages of D50 being 10 +/-0.5 mu m and tap density being 2.35g/cm3The content of S is less than or equal to 0.15%, the content of sodium is less than or equal to 0.01%, the content of Ca, Mg, Fe, Cu, Pd, Cd, Zn, Cr and K is less than or equal to 0.001%, and an SEM picture of a precursor is shown in FIG. 4.
Example 7
A method for preparing a precursor of NCM (5:2:3) by recycling waste ternary lithium batteries is different from the method for preparing the nickel-cobalt-manganese mixed solution in the embodiment 6 in preparation. In the embodiment, potassium hydroxide is used for replacing sodium hydroxide to remove aluminum; sodium pyrosulfite is used as a reducing agent to replace hydrogen peroxide for dissolving and removing aluminum black powder; using ozone to replace hydrogen peroxide to remove iron; ammonia water is used for replacing sodium hydroxide to adjust the pH value to precipitate nickel, cobalt and manganese; the preparation method comprises the following steps of substituting potassium hydroxide for sodium hydroxide in the synthesis process of the precursor:
(1) soaking a sodium chloride solution of a waste ternary lithium ion battery for discharging, drying after discharging, wherein the drying temperature is 200 ℃, the drying time is 5 hours, and then performing air flow sorting and gravity sorting to obtain black powder;
(2) adding pure water into the black powder prepared in the step (1) according to the solid-liquid ratio of 1:5 for pulping, adding potassium hydroxide according to the ratio of n (alkali) to n (aluminum) to 1.5, heating to 80 ℃, reacting for 5 hours, carrying out solid-liquid separation after the reaction is finished, and carrying out filter pressing to obtain the aluminum-removed black powder and the filtrate 1.
(3) Adding pure water into the aluminum-removed black powder according to the solid-to-liquid ratio of 1:3 for washing for 2 times, then adding concentrated sulfuric acid and sodium metabisulfite, controlling the reaction temperature to be 85 ℃, reacting for 6 hours, controlling the pH to be more than 3 after the reaction is finished, then carrying out solid-liquid separation, and carrying out filter pressing to obtain a carbon material and a filtrate 2.
(4) Detecting the copper content in the filtrate 2, wherein the copper content is measured according to the following formula (n) (Fe): iron powder was added at a ratio of n (cu) to 1.2, the reaction temperature was controlled at 80 ℃, the reaction was carried out for 1 hour, and copper was recovered by filtration to obtain a filtrate 3.
(5) And (3) slowly introducing ozone into the filtrate 3, then adjusting the pH to 4.5 by using 3mol/L sodium carbonate solution, controlling the reaction temperature to be 85 ℃, reacting for 3 hours, and filtering to obtain iron hydroxide and filtrate 4.
(6) Adding 15% ammonia water solution into the filtrate 4 to adjust the pH value of the filtrate 4 to 9.5, then filtering to obtain precipitate and filtrate 5, adding pure water into the precipitate according to the solid-to-liquid ratio of 1:3, washing for 3 times, washing for 1h each time at the water temperature of 50 ℃, and removing Li, Ca and Mg in the nickel, cobalt and manganese to obtain nickel, cobalt and manganese oxide precipitate.
(7) Adding pure water into the nickel-cobalt-manganese oxide precipitate according to the proportion of 1:4 for pulping, and then, according to the proportion of m (nickel-cobalt-manganese precipitate): m (concentrated sulfuric acid): and (3) adding concentrated sulfuric acid and hydrogen peroxide in a ratio of m (27% hydrogen peroxide) to 1:1.07:0.6 to prepare a nickel-cobalt-manganese mixed salt solution.
(8) Taking the nickel-cobalt-manganese mixed salt solution prepared in the example 1, supplementing nickel sulfate, cobalt sulfate and manganese sulfate crystals into the mixed salt solution, and preparing the nickel-cobalt-manganese in the solution according to the following proportion: n (Ni) n (Co): n (mn) 5:2:3, and pure water was added to dilute the salt solution to 2 mol/L.
(9) Simultaneously adding 4mol/L potassium hydroxide solution into the reaction kettle, wherein the concentration of ammonia water is 10.5mol/L ammonia water, mixing salt solution, and controlling n (alkali): n (salt) ═ 2.01:1, n (ammonia): n (salt) ═ 1.2, and the flow ratio of the mixed salt solution to the sodium metaaluminate solution is 10: 1.
(10) The NCM523 ternary precursor synthesized by the invention has the advantages of D50 being 3.5 +/-0.5 mu m and tap density being 2.15g/cm3The content of S is less than or equal to 0.15%, the content of potassium is less than or equal to 0.01%, the content of Ca, Mg, Fe, Cu, Pd, Cd, Zn, Cr and Na is less than or equal to 0.001%, and an SEM picture of a precursor is shown in FIG. 5.
Claims (10)
1. A method for preparing a precursor by recycling a waste ternary lithium ion battery is characterized by comprising the following steps,
s1, discharging, crushing, drying and sorting the ternary lithium ion battery to obtain black powder;
s2, soaking the black powder in alkali, and performing solid-liquid separation to obtain aluminum-removed black powder and filtrate 1;
s4, leaching the aluminum black powder by using acid and a reducing agent to remove nickel, cobalt and manganese, and performing solid-liquid separation to obtain a carbon material and a filtrate 2;
s5, adding iron powder into the filtrate 2, and carrying out solid-liquid separation to obtain copper and a filtrate 3;
s6, adding an oxidant into the filtrate 3, adding alkali to adjust the pH value, precipitating ferric hydroxide, and performing solid-liquid separation to obtain ferric hydroxide and a filtrate 4;
s7, adjusting the pH value of the filtrate 4 by using alkali, precipitating nickel, cobalt and manganese, and obtaining nickel, cobalt and manganese oxide and a filtrate 5 after filter pressing and washing;
s8, reversely dissolving the nickel-cobalt-manganese hydroxide to prepare a nickel-cobalt-manganese mixed salt solution;
and S9, preparing salt, and carrying out coprecipitation to synthesize a precursor.
2. The method for recycling the precursors prepared from the waste ternary lithium ion batteries according to claim 1, is characterized in that: in S9, the precursor is a ternary or quaternary precursor, and the chemical general formula of the precursor is as follows: niaCobMncAl1-a-b-c(OH)2Wherein a is more than or equal to 0.3 and less than or equal to 0.96, b is more than 0 and less than or equal to 0.2, c is more than 0 and less than or equal to 0.3, and the tap density of the precursor is 1.6-2.4g/cm3D50 is 3-10 μm; .
3. The method for recycling the precursor prepared by the waste ternary lithium ion battery according to claim 1 or 2 is characterized in that: in S9, the salt concentration of the synthetic precursor is 0.18-0.23mol/L, the alkali is one or two of sodium hydroxide and potassium hydroxide, the alkali concentration is 4-11mol/L, the ammonia water concentration is 10-15mol/L, n (alkali): n (salt) ═ 2.0-2.1, n (ammonia): n (salt) ═ 1-2.
4. The method for recycling the precursors prepared by the waste ternary lithium ion batteries according to the claim 1 or 2, is characterized in that: comprising S10, adding sodium carbonate into the filtrate 5 to precipitate lithium, washing with water, filtering, and recrystallizing to obtain high-purity lithium carbonate.
5. The method for recycling the precursor prepared by the waste ternary lithium ion battery according to claim 1 or 2 is characterized in that: in S2, the black powder is soaked in alkali to remove aluminum, the alkali is one or two of sodium hydroxide and potassium hydroxide, the concentration of the alkali is 0.1-10mol/L, the solid-to-liquid ratio of the alkali leaching is 1:2-1: 10, n (alkali) n (aluminum) is 1-3, the temperature of the alkali leaching is 60-100 ℃, and the leaching time is 3-8 hours.
6. The method for recycling the precursors prepared from the waste ternary lithium ion batteries according to claim 3, is characterized in that: including S3, adding acid into the filtrate 1 to obtain aluminum hydroxide precipitate, washing and filter-pressing the precipitate, adding liquid caustic soda to recover aluminum and preparing sodium metaaluminate; in S3, sulfuric acid is used for adjusting pH to precipitate aluminum, wherein the concentration of the sulfuric acid is 1-4mol/L, the pH value of aluminum hydroxide precipitate is 4-6, the reaction time is 3-5h, the aluminum hydroxide is washed with water for removing impurities, the solid-to-liquid ratio of the washing is 1:1-1:5, the washing is carried out for 2-5 times, the washing temperature is 30-60 ℃, 5-10mol/L sodium hydroxide is added into the aluminum hydroxide, the pH value of the solution is controlled to be more than 11, the reaction time is 3-5h, the reaction temperature is 60-80 ℃, and sodium metaaluminate solution is obtained by filtering.
7. The method for recycling the precursor prepared by the waste ternary lithium ion battery according to claim 1 or 2 is characterized in that: in S4, leaching nickel, cobalt and manganese in the black powder by using acid and a reducing agent, wherein the leaching temperature is 60-90 ℃, the leaching time is 6-12h, the acid is one or more of sulfuric acid, hydrochloric acid and nitric acid, and the reducing agent is one or two of hydrogen peroxide and sodium metabisulfite.
8. The method for recycling the precursor prepared by the waste ternary lithium ion battery according to claim 1 or 2 is characterized in that: in S5, removing copper by adopting iron powder, wherein the adding amount of the iron powder is 1.1-1.5 times of the mass of copper, the reaction temperature is 80-90 ℃, and the reaction time is 1-2 h; in S6, the oxidant is one or two of hydrogen peroxide or ozone, the alkali is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and ammonia water, the pH of the iron-aluminum-removed solution is 3.8-4.5, the reaction temperature is 80-90 ℃, and the reaction time is 3-5 hours; in S7, the alkali is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and ammonia water, the pH value of the nickel-cobalt-manganese precipitate is 7-9.5, the water washing solid-liquid ratio is 1:2-1:5, the water washing time is 1-2h, and the water washing temperature is 30-70 ℃.
9. The method for recycling the precursor prepared by the waste ternary lithium ion battery according to claim 1 or 2 is characterized in that: in S8, concentrated sulfuric acid and hydrogen peroxide are used for reversely dissolving nickel-cobalt-manganese precipitate, wherein m (nickel-cobalt-manganese precipitate): m (concentrated sulfuric acid): m (27% hydrogen peroxide) is 1:1-1.1:0.6-0.7, the solid-to-liquid ratio is 1:2-1:4, and the pH value of the obtained salt solution is 3-4.
10. The method for recycling the precursors prepared from the waste ternary lithium ion batteries according to claim 4, is characterized in that: in S10, lithium-containing wastewater is firstly concentrated, the concentration of lithium after concentration is 15-20g/L, the pH value of the solution is adjusted to be more than 13, the reaction temperature is controlled to be 80-100 ℃, then sodium carbonate is added for precipitating lithium, the molar weight of the sodium carbonate is 1-3 times of that of the lithium, and lithium carbonate is obtained through filtration, water washing and recrystallization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210219092.7A CN114583309A (en) | 2022-03-08 | 2022-03-08 | Method for preparing precursor by recycling waste ternary lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210219092.7A CN114583309A (en) | 2022-03-08 | 2022-03-08 | Method for preparing precursor by recycling waste ternary lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114583309A true CN114583309A (en) | 2022-06-03 |
Family
ID=81777802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210219092.7A Pending CN114583309A (en) | 2022-03-08 | 2022-03-08 | Method for preparing precursor by recycling waste ternary lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114583309A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107653378A (en) * | 2017-08-25 | 2018-02-02 | 金川集团股份有限公司 | The recovery method of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery |
| CN109088115A (en) * | 2018-07-24 | 2018-12-25 | 北京科技大学 | Waste lithium ion cell anode closed matereial cycle prepares tertiary cathode material method |
| CN110040786A (en) * | 2019-04-18 | 2019-07-23 | 甘肃睿思科新材料有限公司 | A kind of method of anode material of lithium battery recycling and reusing |
| CN111261967A (en) * | 2020-01-22 | 2020-06-09 | 宁波容百新能源科技股份有限公司 | Recovery method of waste lithium battery and battery-grade nickel-cobalt-manganese mixed crystal prepared by recovery |
| CN112126783A (en) * | 2020-08-25 | 2020-12-25 | 湖南邦普循环科技有限公司 | Recycling method of iron and aluminum in nickel-cobalt-manganese solution |
| CN112374511A (en) * | 2020-10-17 | 2021-02-19 | 北京科技大学 | Method for preparing lithium carbonate and ternary precursor by recycling waste ternary lithium battery |
-
2022
- 2022-03-08 CN CN202210219092.7A patent/CN114583309A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107653378A (en) * | 2017-08-25 | 2018-02-02 | 金川集团股份有限公司 | The recovery method of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery |
| CN109088115A (en) * | 2018-07-24 | 2018-12-25 | 北京科技大学 | Waste lithium ion cell anode closed matereial cycle prepares tertiary cathode material method |
| CN110040786A (en) * | 2019-04-18 | 2019-07-23 | 甘肃睿思科新材料有限公司 | A kind of method of anode material of lithium battery recycling and reusing |
| CN111261967A (en) * | 2020-01-22 | 2020-06-09 | 宁波容百新能源科技股份有限公司 | Recovery method of waste lithium battery and battery-grade nickel-cobalt-manganese mixed crystal prepared by recovery |
| CN112126783A (en) * | 2020-08-25 | 2020-12-25 | 湖南邦普循环科技有限公司 | Recycling method of iron and aluminum in nickel-cobalt-manganese solution |
| WO2022042228A1 (en) * | 2020-08-25 | 2022-03-03 | 湖南邦普循环科技有限公司 | Method for recycling iron and aluminum in nickel-cobalt-manganese solution |
| CN112374511A (en) * | 2020-10-17 | 2021-02-19 | 北京科技大学 | Method for preparing lithium carbonate and ternary precursor by recycling waste ternary lithium battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111129632B (en) | Method for recycling anode and cathode mixed materials of waste ternary lithium ion battery | |
| CN111206148B (en) | Method for recycling and preparing ternary cathode material by using waste ternary lithium battery | |
| JP7216945B2 (en) | Manganese-lithium separation and pre-extraction solution preparation process in comprehensive recovery of ternary battery waste and method for comprehensive recovery of cobalt-nickel-manganese-lithium elements from ternary battery waste | |
| CN107267759B (en) | A kind of comprehensive recovering process of anode material for lithium-ion batteries | |
| CN108550939B (en) | A method of selective recovery lithium and lithium carbonate is prepared from waste lithium cell | |
| CN113061723B (en) | Method for recovering lithium from waste lithium iron phosphate batteries and preparing iron phosphate | |
| CN111261967A (en) | Recovery method of waste lithium battery and battery-grade nickel-cobalt-manganese mixed crystal prepared by recovery | |
| CN106848470A (en) | A kind of method for reclaiming, preparing tertiary cathode material from waste and old nickel-cobalt-manganese ternary lithium ion battery | |
| CN111254294B (en) | Method for selectively extracting lithium from waste lithium ion battery powder and recovering manganese dioxide through electrolytic separation | |
| CN102088124A (en) | High-purity polymetallic-element solid mixed salt and preparation method and application thereof | |
| WO2022052670A1 (en) | Method for purifying nickel-cobalt-manganese leaching solution | |
| CN113200574A (en) | Method for regenerating lithium-rich manganese-based positive electrode from mixed waste lithium battery | |
| CN107046154B (en) | Method for enhanced reduction leaching of waste ternary lithium battery | |
| CN113106257A (en) | Recycling method of lithium battery waste and application thereof | |
| US20240088468A1 (en) | Method for extracting lithium from waste lithium battery | |
| CN114249313A (en) | Method for recovering battery-grade iron phosphate from waste lithium iron phosphate powder | |
| CN111180819B (en) | Preparation method of battery-grade Ni-Co-Mn mixed solution and battery-grade Mn solution | |
| CN112960705A (en) | Method for recycling quaternary lithium ion battery anode material | |
| CN110498434B (en) | Recovery method and application of lithium ion battery positive electrode active material | |
| CN114933291A (en) | Method for preparing high-purity lithium iron phosphate by using nickel-iron alloy | |
| CN111118311A (en) | Manganese-lithium separation method in comprehensive recovery of ternary battery waste | |
| CN106981699A (en) | A kind of method that lithium is reclaimed from waste lithium iron phosphate battery | |
| CN112342383A (en) | Method for separating and recovering nickel, cobalt, manganese and lithium in ternary waste | |
| CN115784188A (en) | Method for recycling and preparing battery-grade iron phosphate | |
| WO2023093163A1 (en) | Method for recovering lithium battery positive electrode plate |
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 |