CN115074540B - Comprehensive recovery method for valuable components of waste power battery - Google Patents

Comprehensive recovery method for valuable components of waste power battery Download PDF

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CN115074540B
CN115074540B CN202210977779.7A CN202210977779A CN115074540B CN 115074540 B CN115074540 B CN 115074540B CN 202210977779 A CN202210977779 A CN 202210977779A CN 115074540 B CN115074540 B CN 115074540B
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sulfate
nickel
cobalt
solution
lithium
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CN115074540A (en
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邓超群
王海北
李诗丽
邹小平
蒋应平
朱坤娥
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BGRIMM Technology Group Co Ltd
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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
    • 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
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • 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
    • 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
    • C22B47/00—Obtaining manganese
    • 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
    • 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

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  • Engineering & Computer Science (AREA)
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Abstract

The invention belongs to the technical field of waste power battery recovery, and particularly relates to a comprehensive recovery method of valuable components of a waste power battery, which comprises the following steps: (1) Mixing and roasting waste power battery raw materials and sulfate to obtain roasted sand; (2) Carrying out water leaching on the calcine, and filtering to obtain nickel-cobalt-manganese slag and a lithium-rich solution; (3) Acid leaching the nickel-cobalt-manganese slag, and filtering to obtain acid leaching solution; (4) Performing displacement copper removal treatment on the pickle liquor, and filtering to obtain a copper-removed liquor; (5) Carrying out high-temperature impurity removal and optional deep impurity removal on the copper-removed solution to obtain a nickel-containing cobalt manganese sulfate solution; the reaction temperature for removing impurities is 180-250 ℃. The method provided by the invention has the advantages that the lithium/nickel/cobalt/manganese all components in the raw materials of the waste power battery are efficiently recycled, the recovery rate is high, impurities such as iron/aluminum/copper/fluorine/phosphorus/calcium/magnesium are effectively and deeply removed, the battery-grade lithium carbonate and the battery ternary precursor solution can be respectively prepared, and the solid waste is recycled; and the process is simple.

Description

Comprehensive recovery method for valuable components of waste power battery
Technical Field
The invention belongs to the technical field of waste power battery recovery, and particularly relates to a comprehensive recovery method of valuable components of a waste power battery.
Background
The usage amount of the power battery as the heart of a new energy automobile is increasing. Lithium element is used as a key component of the power battery, and the resource supply situation is increased or decreased. In terms of lithium resource supply, although the exploitation of lithium ore is increased, natural resources are sought, and the strategy for resource sustainability development is not met. Therefore, many countries are beginning to spend on low cost, efficient recovery of spent power battery lithium, expecting maximum profit.
For the recovery of waste power battery lithium, a rear-end recovery mode is mostly adopted, for example, CN 111261967A carries out reduction acid leaching on waste lithium batteries to obtain nickel/cobalt/manganese/lithium-containing acid leaching solution, then an alkali reagent is added to precipitate nickel, cobalt and manganese, solid-liquid separation is carried out to obtain a lithium-rich solution, and the recovery of lithium is realized; CN 114231744A discloses that waste lithium batteries and ferric sulfate salt are roasted at a certain temperature, and the roasted product is subjected to water leaching to realize separation and enrichment of nickel/cobalt/manganese/lithium and slag. Although the recovery of lithium can be realized by the several methods, the problems that the consumption of reagents is large, the cost is high due to the simultaneous enrichment of metals such as nickel/cobalt/manganese and the like and lithium, and the direct recovery rate of lithium is low due to the high loss rate of lithium in the separation process of lithium and nickel/cobalt/manganese exist. To solve the problems of the back-end recovery, many patents disclose front-end recovery processes, for example, CN 112993428A and CN 111463475A disclose the use of waste lithium batteries and carbonaceous reducing agents to perform carbothermic reduction roasting at a certain temperature to make lithium exist in the form of lithium carbonate by direct water immersion or CO 2 Water leaching to realize preferential extraction of lithium; although the method is theoretically feasible, the lithium transformation is incomplete in the roasting process and the water solubility of the lithium carbonate is low, so that the recovery rate of lithium is low (below 80 percent), and a large amount of water is consumed to realize the maximum dissolution of the lithium. For another example, CN 111206148A discloses that the waste lithium battery is roasted with ammonium sulfate, potassium bisulfate or sodium bisulfate at a certain temperature, and then the roasted product is subjected to water leaching to realize the separation of lithium from nickel/cobalt/manganese; although the separation of lithium and nickel/cobalt/manganese can be realized, the problems of large environmental pollution (such as ammonia gas generation) and excessive introduction of impurities such as potassium/sodium exist, so that sodium sulfate supersaturated crystals exist in the subsequent lithium carbonate preparation process, a considerable part of lithium is lost in sodium sulfate due to entrainment, and the recovery rate of lithium is seriously reduced.
The waste power battery contains strategic metals such as nickel/cobalt/manganese besides lithium-containing element, and the recovery of the metals cannot be ignored. For the recovery of nickel/cobalt/manganese, the main adopted mode is extraction separation purification, calcium/magnesium impurities are removed, and battery-grade nickel/cobalt/manganese sulfate is respectively obtained, for example, magnesium sulfate is introduced in the roasting lithium extraction process of CN111334664A, although the preferential extraction of lithium can be realized, a large amount of magnesium impurities are additionally added, the burden of subsequent extraction and impurity removal is increased, and the cost is increased; the technical route shows that an extraction line is separately added on the recovery of magnesium, and the extraction line is added on the lithium extraction, so that the waste of the internal circulation process is caused. The method mainly innovatively follows the traditional route of preparing battery-grade nickel/cobalt sulfate by using nickel-cobalt ore, while the impurity content of the waste power battery is far lower than that of the nickel-cobalt ore, such as calcium/magnesium/silicon. That is, aiming at a waste power battery system, the impurity removal and the nickel/cobalt/manganese recovery can directly prepare the nickel/cobalt/manganese precursor mixed solution for the battery without adopting an extraction route; the prior art is complex.
In a word, how to obtain a method for recovering a waste power battery with high lithium recovery rate, high nickel, cobalt and manganese recovery efficiency and high impurity removal rate under the conditions of process simplification and environmental protection is a problem to be solved urgently in the field.
Disclosure of Invention
The invention aims to overcome the defects that the recovery rate of lithium, nickel, cobalt and manganese and the removal rate of impurities are required to be improved and the process flow is complex in the prior art, and provides a comprehensive recovery method of valuable components of a waste power battery, wherein the method is used for efficiently recovering lithium/nickel/cobalt/manganese all components in the raw materials of the waste power battery, the recovery rate of lithium/nickel/cobalt/manganese is high, the impurities such as iron/aluminum/copper/fluorine/phosphorus/calcium/magnesium are effectively and deeply removed, and battery-grade lithium carbonate and a battery ternary precursor solution can be respectively prepared, so that solid waste is recycled; and the process is simple.
In order to realize the aim, the invention provides a comprehensive recovery method of valuable components of a waste power battery, which comprises the following steps:
(1) Mixing and roasting waste power battery raw materials and sulfate to obtain roasted sand;
(2) Carrying out water leaching on the calcine, and filtering to obtain nickel-cobalt-manganese slag and a lithium-rich solution;
(3) Acid leaching the nickel-cobalt-manganese slag, and filtering to obtain acid leaching solution;
(4) Performing displacement copper removal treatment on the pickle liquor, and filtering to obtain a copper-removed liquor;
(5) Carrying out high-temperature impurity removal and optional deep impurity removal on the copper-removed solution to obtain a nickel-containing cobalt-manganese sulfate solution;
wherein the high-temperature impurity removal process comprises the following steps: in the presence of oxygen, adding sodium sulfate for impurity removal reaction, wherein the use amount of the sodium sulfate is 1/3-1 time of the molar amount of aluminum in the system solution by mol, the pH value of the solution is controlled to be 1-3, the impurity removal reaction temperature is 180-250 ℃, and the impurity removal reaction time is 1-4h.
In some preferred embodiments of the present invention, in step (1), the amount of the sulfate is 1 to 3 times the theoretical amount of the lithium required for the reaction in the raw material of the waste power battery, on a molar basis.
In some preferred embodiments of the present invention, in step (1), the sulfate salt comprises a first sulfate salt and optionally a second sulfate salt, the first sulfate salt comprises at least one of manganese sulfate, nickel sulfate and cobalt sulfate, and the second sulfate salt comprises at least one of iron sulfate, aluminum sulfate and sodium bisulfate.
More preferably, the first sulfate is used in an amount of 0.9 to 1.2 times the theoretical amount of lithium required for reaction in the waste power battery raw material, and the second sulfate is used in an amount of 0.05 to 0.2 times the theoretical amount of lithium required for reaction in the waste power battery raw material, on a molar basis.
The raw materials of the waste power battery comprise anode materials.
In some preferred embodiments of the present invention, in step (1), the calcination conditions include: the roasting temperature is 500-1000 ℃, and the roasting time is 1-6 h.
In some preferred embodiments of the present invention, in the step (2), the water leaching conditions include: the liquid-solid ratio is 2-10 mL/g, the water immersion temperature is 20-80 ℃, and the water immersion time is 0.5-2 h.
In some preferred embodiments of the present invention, step (2) further comprises: before the water leaching, the calcine is ground, and the grinding enables the particle size of the calcine to be more than 200 meshes.
In some preferred embodiments of the present invention, in the step (3), the acid leaching process comprises: adding sulfuric acid solution, and then adding hydrogen peroxide for acid leaching reaction.
Preferably, the dosage of the sulfuric acid in the sulfuric acid solution is 1-1.2 times of the theoretical dosage of the acid required by the reaction of the nickel-cobalt-manganese slag by mol, and the liquid-solid ratio is 3-10 mL/g.
Wherein, the acid leaching reaction temperature is 30-90 ℃, the acid leaching reaction time is 1-3h, and the end point pH is controlled at 1.5-3.
Wherein, the dosage of the hydrogen peroxide is preferably 3-8vol.% of the system solution.
In some preferred embodiments of the present invention, in the step (4), the process of replacing copper removal treatment comprises: adding a copper removing agent for reaction at the temperature of 30-90 ℃ for 1-4h.
Preferably, the dosage of the copper removing agent is 1 to 2 times of the theoretical dosage required by the copper replacement reaction in the pickle liquor by mol.
Preferably, the copper removing agent is at least one of iron powder, nickel powder and manganese powder.
In the step (5), the reaction temperature for removing impurities is preferably 210 to 250 ℃.
In the step (5), preferably, the amount of the sodium sulfate is 0.4 to 0.6 times of the molar amount of the aluminum in the system solution by mol.
In some preferred embodiments of the present invention, in the high-temperature impurity removal in the step (5), oxygen is introduced at such a flow rate that the oxygen pressure is maintained at 0.1 to 1 MPa.
In some preferred embodiments of the present invention, in the step (5), the deep impurity removal process includes: the resin is firstly subjected to fluorine removal, and then neutralization, precipitation and impurity removal are carried out.
More preferably, the process of resin defluorination comprises: firstly, adding a pH regulator to control the pH value of the solution to be 3-5, and then introducing the solution into resin; wherein the resin is LX 760 or LX 860.
More preferably, the process of neutralizing, precipitating and removing impurities comprises the following steps: adding alkali liquor to control the pH value of the system to be 5.5-6.5.
In some preferred embodiments of the present invention, the method further comprises the steps of: (6) Purifying, neutralizing and precipitating the lithium-rich solution obtained in the step (2), and filtering to obtain purified lithium liquid and neutralized slag; and (4) using the purified lithium liquid to prepare battery-grade lithium carbonate, and optionally circulating the neutralized slag to the step (3) to perform acid leaching together with the nickel-cobalt-manganese slag.
According to the technical scheme, particularly, a process route of acid leaching, displacement copper removal treatment, high-temperature impurity removal and optional deep impurity removal is adopted for the nickel-cobalt-manganese slag, so that the impurities such as iron/aluminum/copper/fluorine/calcium/magnesium can be deeply removed; meanwhile, the recovery rate of lithium, nickel, cobalt and manganese is improved. Wherein, the edulcoration in the high temperature edulcoration process includes: 1) Sodium sulfate and aluminum sulfate in the system solution generate sodium alum which is difficult to dissolve in water at high temperature; 2) Reacting ferric iron at high temperature to generate hematite; 3) Fluorine and calcium/magnesium in the solution are easy to generate calcium fluoride/magnesium fluoride which is difficult to dissolve in water at high temperature; 4) The generated sodium alum and hematite have certain strong adsorption capacity on fluorine, and directly adsorb and remove the fluorine, thereby realizing deep impurity removal of calcium/magnesium and preliminary removal of iron/aluminum/fluorine in a synergistic manner. The high-temperature impurity removal method can remove various impurities such as iron/aluminum/fluorine/calcium/magnesium in one step, compared with the traditional method for removing iron and aluminum by neutralization, the method has the outstanding advantages of no addition of a neutralizing agent, less slag, low loss of main metal nickel/cobalt/manganese and the like, and solves the problem that calcium and magnesium are difficult to deeply remove by a normal-temperature chemical precipitation method by utilizing the properties of easy generation and low solubility of calcium fluoride/magnesium fluoride at high temperature.
The method can realize high recovery rate of nickel, cobalt and manganese and preparation of the battery-grade nickel-containing cobalt-manganese sulfate solution, the recovery rate of lithium, nickel, cobalt and manganese can be more than 99% in the whole process, solid waste recycling of waste power batteries is realized, and the battery-grade lithium carbonate and the battery-grade nickel-containing cobalt-manganese sulfate solution can be prepared respectively.
In the preferred deep impurity removal scheme of the invention, resin fluorine removal is firstly carried out, and then neutralization precipitation impurity removal is carried out; wherein, 1) fluorine and nickel/cobalt/manganese have essential difference on valence state, fully utilize resin to select the characteristic of the specificity to the valence state, realize the deep edulcoration of fluorine; 2) The neutralization precipitation mainly carries out deep removal on the residual iron/aluminum; thereby further deeply removing impurities.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
FIG. 1 is a process flow diagram of the process of the present invention.
Fig. 2 is an XRD phase analysis of the calcine and the nickel cobalt manganese slag of example 1 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The invention provides a comprehensive recovery method of valuable components of a waste power battery, which comprises the following steps:
(1) Mixing and roasting waste power battery raw materials and sulfate to obtain roasted sand;
(2) Carrying out water leaching on the calcine, and filtering to obtain nickel-cobalt-manganese slag and a lithium-rich solution;
(3) Acid leaching is carried out on the nickel-cobalt-manganese slag, and acid leaching solution is obtained through filtering;
(4) Performing displacement copper removal treatment on the pickle liquor, and filtering to obtain a copper-removed liquor;
(5) And carrying out high-temperature impurity removal and optional deep impurity removal on the copper-removed solution to obtain the nickel-containing cobalt manganese sulfate solution.
Wherein the high-temperature impurity removal process comprises the following steps: in the presence of oxygen, adding sodium sulfate to perform impurity removal reaction, wherein the dosage of the sodium sulfate is 1/3-1 time of the molar quantity of aluminum in a system solution (also can be called that the molar ratio of sodium to aluminum is 1/3-1) by mol, the pH of the solution is controlled to be 1-3, the impurity removal reaction temperature is 180-250 ℃, and the impurity removal reaction time is 1-4h.
The waste power battery raw material comprises a positive electrode material. The invention has no limitation on the source of the waste power battery raw material, for example, the waste power battery raw material can be battery black powder, and the battery black powder is obtained by discharging, disassembling, crushing and separating the waste power battery and is mainly an active anode material; in some embodiments, the battery black powder is prepared by a process comprising: the waste ternary power battery is subjected to pretreatment such as discharging, disassembling, crushing, separating and the like, a current collector, a diaphragm, electrolyte and the like are removed, the introduction of impurities is reduced, and pure black powder containing nickel/cobalt/manganese/lithium/negative graphite is obtained. The waste power battery raw material can also be anode powder which is mainly derived from unqualified products produced in the production process of the anode material. The type of waste power battery may be a nickel cobalt manganese/aluminum ternary lithium battery, a nickel/cobalt/manganese unitary or binary lithium battery.
The temperature of the impurity removal reaction is 180-250 ℃, and can be 180, 190, 200, 210, 220, 230, 240, 250 ℃ and the like. In some embodiments, the temperature of the impurity removal reaction is preferably in the range of 210 to 250 ℃.
Preferably, the amount of the sodium sulfate is 1/3 to 1 time of the molar amount of the aluminum in the system solution, for example, 1/3, 0.4, 0.5, 0.6, 2/3, 0.7, 0.8, 0.9, 1 time, etc.; and in some embodiments preferably from 0.4 to 0.6 times.
According to the invention, the roasting-water leaching process of the steps (1) - (2) can realize preferential lithium extraction, so that the aim of separating lithium from nickel/cobalt/manganese is fulfilled, li and P in the raw materials can be efficiently removed, and impurity removal operation is not required in the subsequent process, so that valuable components such as nickel, cobalt and manganese and the like can be efficiently recovered in the subsequent step.
In some preferred embodiments of the present invention, in step (1), the sulfate salt comprises a first sulfate salt and optionally a second sulfate salt, the first sulfate salt comprises at least one of manganese sulfate, nickel sulfate and cobalt sulfate, and the second sulfate salt comprises at least one of iron sulfate, aluminum sulfate and sodium bisulfate. The invention selects nickel sulfate/cobalt sulfate/manganese as sulfate or main sulfate in the roasting process, is different from the prior art which only adopts sulfate such as ferric sulfate/ammonium sulfate/sodium bisulfate/potassium bisulfate and the like, can realize preferential extraction of lithium, has the preferential extraction rate of the lithium of more than 99 percent, does not introduce a large amount of foreign metal impurities (such as sodium and potassium), and avoids the dilemma that impurities and lithium in a lithium-rich water solution are difficult to separate and are seriously carried. Compared with the carbon thermal reduction lithium extraction commonly adopted in the prior art, the method can greatly reduce the water consumption in the water leaching process, improve the lithium content of the obtained solution, for example, the lithium content can be improved from 2g/L to 8g/L under the same condition, reduce the liquid-solid ratio, and the lithium content can even reach 10 g/L and above.
The manganese sulfate, nickel sulfate, cobalt sulfate, iron sulfate, aluminum sulfate, sodium bisulfate may be introduced in the form of various corresponding compounds and hydrates, and may be, for example, manganese sulfate hydrate, nickel sulfate hexahydrate, cobalt sulfate heptahydrate, etc.
The skilled person can select the sulfate according to the type of the battery, preferably the metal species of the sulfate is the same as the metal elements contained in the battery; for example, in the case of a lithium cobalt oxide battery, cobalt sulfate is preferred for preferential lithium extraction in view of reducing the subsequent impurity removal step.
Preferably, the sulfate salt comprises a first sulfate salt including at least one of manganese sulfate, nickel sulfate, and cobalt sulfate, and a second sulfate salt including at least one of iron sulfate, aluminum sulfate, and sodium bisulfate. According to the preferred scheme, a small amount of ferric sulfate, aluminum sulfate and sodium bisulfate are added to promote the rapid cracking of the layered structure, so that lithium exists in a lithium sulfate form, nickel/cobalt/manganese exists in a sulfate form firstly and then reacts with lithium oxide to be converted into nickel/cobalt/manganese oxide again, the phase conversion of a lithium compound is promoted, the phase conversion of the lithium compound is promoted, the dosage of the first sulfate can be reduced, and the preferential extraction rate of lithium is further improved.
The step (1) can remove phosphorus to the maximum extent. Phosphorus in the raw materials of the waste power batteries mainly exists in the form of electrolyte lithium hexafluorophosphate, and PF is easily generated in the roasting process of the step (1) 5 And solid LiF, thereby achieving removal of phosphorus.
Moreover, since the positive active material of the power battery is basically in a layered structure, specifically, a hexagonal crystal structure, it can be understood that a nickel/cobalt/manganese oxide and a lithium oxide form a two-dimensional plane, and lithium ions can move back and forth in the two-dimensional plane during charging and discharging processes. Then, taking manganese sulfate as an example, in the roasting process of step (1), the standard gibbs free energy of the reaction between nickel oxide/cobalt oxide and sulfate is positive, and the standard gibbs free energy of the reaction between lithium oxide and sulfate is negative; namely, lithium oxide and sulfate can spontaneously react at the roasting temperature to generate lithium sulfate which is easy to dissolve in water and manganese oxide which is difficult to dissolve in water, nickel and cobalt exist in the form of oxides, and nickel, cobalt and manganese can be separated from lithium by performing the water leaching in the step (2). When nickel sulfate is used as sulfate to react with cobalt/manganese/lithium oxide, gibbs free energy of standard reaction of nickel sulfate and lithium/cobalt/manganese oxide is less than 0, and the reaction is carried out spontaneously, but the degree of reaction of cobalt/manganese sulfate and lithium oxide is far higher than that of nickel sulfate and cobalt/manganese oxide; in other words, the roasted product is substantially free of cobalt/manganese sulphate as long as lithium oxide is present in the material. The addition of a small amount of ferric sulfate, aluminum sulfate or sodium bisulfate can promote the rapid cracking of the layered structure, so that lithium exists in the form of lithium sulfate, and nickel/cobalt/manganese exists in the form of sulfate firstly and then reacts with lithium oxide to be converted into nickel/cobalt/manganese oxide again, thereby promoting the phase conversion of lithium compounds. And (3) subsequently, directly carrying out water leaching in the step (2) on the roasted material, and realizing rapid preferential extraction of Li. The reaction principle of cobalt sulfate as sulfate with cobalt/manganese/lithium oxide is similar, and will not be described in detail.
In some preferred embodiments of the present invention, in step (1), the amount of the sulfate is 1 to 3 times the theoretical amount of the lithium required for the reaction in the raw material of the waste power battery, on a molar basis. It is understood that the amount of sulfate used is the total amount and is the molar amount of sulfate required to react with the molar amount of lithium in the waste power cell feedstock, by which is meant that lithium oxide reacts with the sulfate to form lithium sulfate. According to some embodiments of the present invention, the sulfate is added in a theoretical amount entirely in conjunction with the lithium rich solution composition, and the solution is substantially free of Ni, co, mn impurities, i.e., the sulfate reacts substantially with the lithium oxide. The leaching rate of lithium is more than 99.38 percent based on slag.
In some preferred embodiments of the invention, the first sulfate is used in an amount of 0.9 to 1.2 times the theoretical amount of lithium required for reaction in the waste power battery raw material, and the second sulfate is used in an amount of 0.05 to 0.2 times the theoretical amount of lithium required for reaction in the waste power battery raw material, on a molar basis. The preferable scheme is more favorable for improving the preferential extraction rate of lithium.
In some preferred embodiments, in step (1), the calcination conditions include: the roasting temperature is 500-1000 ℃, and the roasting time is 1-6 h.
In the step (2), the water leaching is used for preferentially leaching the lithium in the calcine to enrich the lithium in a lithium-rich solution, so that the subsequent high-efficiency extraction of nickel, cobalt and manganese is facilitated.
In some preferred embodiments of the present invention, the water leaching conditions include: the liquid-solid ratio is 2-10 mL/g, the water immersion temperature is 20-80 ℃, and the water immersion time is 0.5-2 h.
In some preferred embodiments of the present invention, step (2) further comprises: grinding the calcine before the water leaching, wherein the grinding enables the particle size of the calcine to be more than 200 meshes.
In the step (2), the preferential extraction rate of Li is more than 99.8%, and the content of lithium in the nickel-cobalt-manganese slag is less than 0.01% by mass.
According to the invention, the nickel-cobalt-manganese slag is subjected to the process route of acid leaching, replacement copper removal treatment, high-temperature impurity removal and optional deep impurity removal in the steps (3) to (5), so that impurities such as iron, aluminum, copper, fluorine, calcium, magnesium and the like can be deeply removed, and a high-concentration battery-grade nickel-cobalt-manganese sulfate solution can be prepared.
In some preferred embodiments of the present invention, in the step (3), the acid leaching process comprises: adding acid solution, and then adding hydrogen peroxide for acid leaching reaction. The acid solution is preferably a sulfuric acid solution.
Preferably, the dosage of the sulfuric acid in the sulfuric acid solution is 1-1.2 times of the theoretical dosage of the acid required by the reaction of the nickel-cobalt-manganese slag by mol, and the liquid-solid ratio is 3-10 mL/g. It is understood that the dosage of the sulfuric acid is the molar amount of the sulfuric acid required for acid leaching reaction of nickel, cobalt and manganese elements in the nickel, cobalt and manganese slag.
Wherein, the acid leaching reaction temperature is 30-90 ℃, the acid leaching reaction time is 1-3h, and the end point pH is controlled to be 1.5-3. It is understood that the end point pH is controlled to be 1.5 to 3, and can be controlled by the amount of acid added (the amount of the sulfuric acid solution used) and the reaction time, and studies have shown that the end point pH can achieve the optimum acid leaching effect within the above range.
The invention adds hydrogen peroxide for partial oxidation, which is beneficial to leaching valuable component metals. Wherein, the dosage of the hydrogen peroxide is preferably 3-8vol.% of the system solution.
In some preferred embodiments of the present invention, in the step (4), the process of replacing copper removal treatment comprises: adding a copper removing agent for reaction at the temperature of 30-90 ℃ for 1-4h.
Preferably, the dosage of the copper removing agent is 1 to 2 times of the theoretical dosage required by the copper replacement reaction in the pickle liquor by mol. It will be appreciated that the amount of copper removal agent used is based on the molar amount of copper in the pickle liquor required for the displacement reaction to take place on a molar basis.
Preferably, the copper removing agent is at least one of iron powder, nickel powder and manganese powder.
In the step (5), oxygen is used for oxidizing ferrous iron into ferric iron again and further precipitating and separating out in impurity removal, so that iron impurities are removed; wherein the ferrous iron part is obtained by reducing ferric iron in the replacement copper removal treatment in the step (4), and the ferrous iron is not beneficial to removing iron during high-temperature impurity removal.
In some preferred embodiments of the present invention, in the high-temperature impurity removal in the step (5), oxygen is introduced at such a flow rate that the oxygen pressure is maintained at 0.1 to 1 MPa.
In step (5), the following impurity removal process takes place simultaneously: 1) Sodium sulfate and aluminum sulfate in the system solution generate sodium alum which is difficult to dissolve in water at high temperature; 2) Reacting ferric iron at high temperature to generate hematite; 3) The generated sodalum and hematite have certain strong adsorption capacity on fluorine, and directly adsorb and remove fluorine; 4) Fluorine in the solution reacts with calcium/magnesium to form calcium fluoride/magnesium fluoride which is insoluble in water. The impurity removal process realizes the synchronous iron/aluminum/fluorine synergistic impurity removal process and the calcium/magnesium deep impurity removal process, namely, the removal of various impurities such as iron/aluminum/fluorine/calcium/magnesium in one step is realized.
In the step (5), the pH value of the solution is controlled to be 1-3, the pH value can be controlled by alkali solution before or after the sodium sulfate is added, for example, the pH value can be sodium hydroxide solution or ammonia water, and the mass concentration of the alkali solution is preferably 3-30%.
In some preferred embodiments of the present invention, in the step (5), the deep impurity removal process includes: the resin is firstly subjected to fluorine removal, and then neutralization, precipitation and impurity removal are carried out.
More preferably, the process of resin defluorination comprises: firstly, adding a pH regulator to control the pH value of the solution to be 3-5, and then introducing the solution into resin; wherein the resin is LX 760 or LX 860.
More preferably, the process of neutralizing, precipitating and removing impurities comprises the following steps: adding alkali liquor to control the pH value of the system to be 5.5-6.5. The alkali solution may be, for example, sodium hydroxide solution or ammonia water, and the mass concentration of the alkali solution is preferably 3 to 30%.
In some preferred embodiments of the invention, the method further comprises the steps of: (6) Purifying, neutralizing and precipitating the lithium-rich solution obtained in the step (2), and filtering to obtain purified lithium liquid and neutralized slag; and (4) using the purified lithium liquid to prepare battery-grade lithium carbonate, and optionally circulating the neutralized slag to the step (3) to perform acid leaching together with the nickel-cobalt-manganese slag. The purification neutralization precipitation can neutralize and precipitate the impurities such as unreacted sulfate (such as manganese sulfate) in the lithium-rich solution obtained in the step (2) in the roasting process, and the obtained neutralization slag can realize the ionic enrichment of nickel, cobalt and manganese after being circulated to the step (3).
In some embodiments, the process of using the purified lithium solution to prepare battery-grade lithium carbonate may include: deep impurity removal, lithium carbonate precipitation, carbonization refining and heating cracking are sequentially adopted. Which is conventional in the art and will not be described further herein.
The purification in step (6) can be performed by one skilled in the art using purification methods known in the art, for example, the purification may include: adding alkali liquor to control the pH value, so that the total content of nickel, cobalt and manganese in the purified lithium liquid is lower than 10 ppm. Preferably, the lye here can be a sodium hydroxide solution with a mass fraction of 5 to 30%, but of course other lye can be used as long as the above-mentioned object is achieved.
The present invention is further illustrated in detail below with reference to specific examples.
Example 1
A comprehensive recovery method for valuable components of a waste power battery is shown in figure 1 and specifically comprises the following steps:
(1) The method comprises the following steps of performing pretreatment such as discharging, disassembling, crushing and separating on a waste ternary power battery, removing a current collector, a diaphragm, electrolyte and the like, reducing the introduction of impurities, and obtaining relatively pure battery black powder containing nickel, cobalt, manganese and lithium and negative electrode graphite;
weighing battery black powder and manganese sulfate monohydrate, finely grinding, uniformly mixing, placing in a muffle furnace, and roasting at 600 ℃ for 3h to obtain roasted sand. By mol, the dosage of manganese sulfate in manganese sulfate monohydrate is 1.2 times of the theoretical dosage required by lithium reaction in the battery black powder.
(2) And (3) finely grinding the roasted sand to be more than 200 meshes, adding water, stirring and leaching, controlling the leaching temperature to be 60 ℃, controlling the solid-to-solid ratio of a leaching solution to be 5 mL/g and the time to be 1h, and carrying out liquid-solid separation to obtain a lithium-rich solution and nickel-cobalt-manganese slag. In the process, the preferential extraction rate of Li is more than 99.8 percent, and the content of lithium in the nickel-cobalt-manganese slag is less than 0.01 percent. The XRD phase analysis of the calcine and the nickel-cobalt-manganese slag is shown in fig. 2, and it can be seen that lithium in the calcine exists in the form of lithium sulfate, and the phase disappears in the nickel-cobalt-manganese slag, i.e. after the battery black powder is roasted and leached in water, lithium is leached and enriched in the water leaching solution in the form of lithium sulfate, thus realizing the selective separation from nickel/cobalt/manganese.
(3) Adding a sulfuric acid solution into the nickel-cobalt-manganese slag for acid leaching, wherein the liquid-solid ratio in the acid leaching process is controlled to be 4mL/g, the molar amount of 98wt% concentrated sulfuric acid is 1.05 times of the theoretical amount of the nickel-cobalt-manganese slag, then adding hydrogen peroxide, wherein the acid leaching temperature is 60 ℃, the amount of the hydrogen peroxide is determined according to the leaching rate of nickel/cobalt/manganese, the amount of the hydrogen peroxide is 5 vol% of the system solution, the reaction time is 2h, and the pH at the end of the reaction is controlled to be 2-3; filtering to obtain pickle liquor.
(4) In the process of copper removal by displacement of the pickle liquor obtained in the step (3), iron powder is selected for copper removal by displacement, the usage amount is 1.1 times of the theoretical amount required by copper displacement reaction in the pickle liquor by molar weight, the reaction temperature is 50 ℃, and the time is 1h; and obtaining the solution after copper removal.
(5) Then, removing impurities at high temperature, controlling the pH of the solution after copper removal to be about 2, adding sodium sulfate according to the sodium-aluminum molar ratio of 1.
(6) Then carrying out deep impurity removal, including resin deep fluorine removal and neutralization precipitation deep impurity removal, wherein in the resin deep fluorine removal, the pH value of the solution is controlled to be about 3, and then the solution is introduced into resin LX 760 to obtain iron and aluminum fluorine removal liquid; and then neutralizing the precipitate, and controlling the pH value to be 5.5-6 to obtain the battery-grade nickel-cobalt-manganese solution.
The content of Fe/Al/Cu/F/Ca/Mg in each process is shown in the following table 1, wherein Li/P is removed in the roasting-water leaching process, and impurity removal operation is not needed in the subsequent process.
TABLE 1
Impurity element Fe Al Cu F Ca Mg
Pickle liquor (g/L) 0.13 3.30 0.10 1.29 0.05 0.04
Liquid after copper removal (g/L) 0.20 3.28 1×10 -4 1.30 0.05 0.04
Iron and aluminum fluoride removing liquid (g/L) 0.03 0. 80 1×10 -4 0.08 3.58×10 -3 5.72×10 -3
Battery grade nickel cobalt manganese solution (mg/L) 0.01 0.06 0.10 0.05 3.65 5.52
In the whole impurity removal process of the steps (5) - (6), the loss rates of nickel, cobalt and manganese are respectively 1.8%, 0.8% and 0.3%, the total content of nickel, cobalt and manganese in the obtained battery-grade nickel-cobalt-manganese solution is 101 g/L, and a qualified ternary precursor can be prepared by properly proportioning. The recovery rates of lithium, nickel, cobalt and manganese are respectively 99.5, 97.2, 98.5 and 99.1 percent.
Example 2
The process was carried out as described in example 1, except that the reaction temperature for the high-temperature impurity removal in step (5) was varied, specifically 250 ℃. Accordingly, the Fe/Al/Cu/F/Ca/Mg contents of the subsequent processes are shown in Table 2 below.
TABLE 2
Impurity element Fe Al Cu F Ca Mg
De-ironing aluminium fluorine liquid (g/L) 0.04 0. 08 0.1×10 -3 0.06 2.04×10 -3 3.18×10 -3
Battery grade nickel cobalt manganese solution (mg/L) 0.02 0.04 0.10 0.10 2.65 3.22
In the whole impurity removal process of the steps (5) - (6), the loss rates of nickel, cobalt and manganese are respectively 0.3%, 0.2% and 0.1%, the total content of nickel, cobalt and manganese in the obtained battery-grade nickel-cobalt-manganese solution is 109g/L, and the qualified ternary precursor can be prepared by properly blending the proportions. The recovery rates of lithium, nickel, cobalt and manganese are respectively 99.3, 99.2, 99.4 and 99.6 percent.
Example 3
The process was carried out in accordance with example 1, except that the reaction temperature for the high-temperature impurity removal in step (5) was varied, specifically 220 ℃. Accordingly, the Fe/Al/Cu/F/Ca/Mg contents of the subsequent processes are shown in Table 3 below.
TABLE 3
Impurity element Fe Al Cu F Ca Mg
Iron and aluminum fluoride removing liquid (g/L) 0.02 0.20 1×10 -4 0.05 3.39×10 -3 5.29×10 -3
Battery grade nickel cobalt manganese solution (mg/L) 0.01 0.1 0.10 0.13 3.40 5.40
In the whole impurity removal process of the steps (5) - (6), the loss rates of nickel, cobalt and manganese are respectively 0.4%, 0.3% and 0.2%, the total content of nickel, cobalt and manganese in the obtained battery-grade nickel-cobalt-manganese solution is 107g/L, and a qualified ternary precursor can be prepared by properly proportioning. The recovery rates of lithium, nickel, cobalt and manganese are respectively 99.4, 99.0, 99.4 and 99.4 percent.
Example 4
The procedure was carried out with reference to example 3, except that, in the high-temperature impurity removal of step (5), sodium sulfate was added in a molar ratio of sodium to aluminum of 1.4. Accordingly, the Fe/Al/Cu/F/Ca/Mg contents of the subsequent processes are shown in Table 4 below.
TABLE 4
Impurity element Fe Al Cu F Ca Mg
Iron and aluminum fluoride removing liquid (g/L) 0.01 0.05 1×10 -4 0.060 4.33×10 -3 4.28×10 -3
Battery grade nickel cobalt manganese solution (mg/L) 0.01 0.01 0.08 0.03 4.14 4.52
In the whole impurity removal process of the steps (5) - (6), the loss rates of nickel, cobalt and manganese are respectively 0.3%, 0.2% and 0.2%, the total content of nickel, cobalt and manganese in the obtained battery-grade nickel-cobalt-manganese solution is 107g/L, and the qualified ternary precursor can be prepared by properly proportioning. The recovery rates of lithium, nickel, cobalt and manganese are respectively 99.4, 99.2, 99.4 and 99.6 percent.
Example 5
The procedure was carried out with reference to example 3, except that, in the high-temperature impurity removal of step (5), sodium sulfate was added in a molar ratio of sodium to aluminum of 2. Accordingly, the Fe/Al/Cu/F/Ca/Mg contents of the subsequent processes are shown in Table 5 below.
TABLE 5
Impurity element Fe Al Cu F Ca Mg
Iron and aluminum fluoride removing liquid (g/L) 0.04 0.0 4 1×10 -4 0.05 4.58×10 -3 4.72×10 -3
Battery grade nickel cobalt manganese solution (mg/L) 0.01 0.01 0.10 0.04 4.67 4.37
In the whole impurity removal process of the steps (5) - (6), the loss rates of nickel, cobalt and manganese are respectively 0.3%, 0.2% and 0.2%, which is not much different from that of the embodiment 4, but the consumption of the sodium sulfate reagent is high under the condition, so that the sodium content of the nickel-cobalt-manganese solution is high. And the total content of nickel, cobalt and manganese in the obtained battery-grade nickel, cobalt and manganese solution is 106 g/L, and a qualified ternary precursor can be prepared by properly proportioning. The recovery rates of lithium, nickel, cobalt and manganese are respectively 99.3, 99.1 and 99.2 percent.
Comparative example 1
The procedure was carried out in accordance with the procedure of example 1, except that the reaction temperature in the high-temperature impurity removal in the step (5) was 130 ℃. Accordingly, the Fe/Al/Cu/F/Ca/Mg contents of the AlFeFe-F removing liquid are shown in the following Table 1-1.
TABLE 1-1
Impurity element Fe Al Cu F Ca Mg
Iron and aluminum fluoride removing liquid (g/L) 0.12 3.24 1×10 -4 1.27 0.045 0.037
In the comparative example, the high-temperature impurity removal temperature is 130 ℃, aluminum sulfate and sodium sulfate basically do not react, and iron does not generate hematite, namely, fe/Al/Cu/F/Ca/Mg and other impurities cannot achieve a good removal effect at the temperature.
Comparative example 2
The procedure was carried out in accordance with the procedure of example 1, except that the reaction temperature in the high-temperature impurity removal in the step (5) was 280 ℃. Accordingly, the Fe/Al/Cu/F/Ca/Mg contents of the subsequent processes are shown in tables 1-2 below.
Tables 1 to 2
Impurity element Fe Al Cu F Ca Mg
Iron and aluminum fluoride removing liquid (g/L) 0.02 0. 05 1×10 -4 0.08 3.32×10 -3 5.42×10 -3
Battery grade nickel cobalt manganese solution (mg/L) 0.01 0.06 0.10 0.11 3.05 5.12
In the whole impurity removal process of the steps (5) - (6), the total loss rate of nickel, cobalt and manganese is lower than 0.5%, the total content of nickel, cobalt and manganese in the obtained battery-grade nickel-cobalt-manganese solution is 106 g/L, and a qualified ternary precursor can be prepared by properly proportioning. The recovery rates of lithium, nickel, cobalt and manganese are respectively 99.3, 99.2, 99.0 and 99.4 percent. Although the same effect can be basically achieved at the temperature, the production cost and the operation risk coefficient are increased due to the overhigh temperature.
According to the embodiment and the comparative example, the embodiment of the scheme of the invention can realize deep removal of impurities such as iron/aluminum/copper/fluorine/calcium/magnesium; meanwhile, the recovery rate of lithium, nickel, cobalt and manganese is improved; and the production cost is relatively low.
Furthermore, the embodiment 1 and the embodiments 2 to 3 show that the scheme of optimizing the high-temperature impurity removal reaction temperature is more favorable for deeply removing impurities such as iron/aluminum/copper/fluorine/calcium/magnesium and the like, and is more favorable for improving the recovery rate of nickel, cobalt and manganese. Through the embodiment 3 and the embodiments 4 to 5, it is known that the embodiment 4 with the appropriate amount of sodium sulfate for high-temperature impurity removal is preferably adopted, so that the deep removal of impurities such as iron/aluminum/copper/fluorine/calcium/magnesium is facilitated, the cost is low, new elements such as sodium are prevented from being introduced into a nickel-cobalt-manganese solution as far as possible, and the recovery rate and the purity of nickel-cobalt-manganese are improved.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (8)

1. A comprehensive recovery method for valuable components of waste power batteries is characterized by comprising the following steps:
(1) Mixing and roasting waste power battery raw materials and sulfate to obtain roasted sand; the sulfate comprises a first sulfate, and the first sulfate comprises at least one of manganese sulfate, nickel sulfate and cobalt sulfate; the sulfate salt further comprises a second sulfate salt comprising at least one of ferric sulfate, aluminum sulfate, and sodium bisulfate; in terms of molar quantity, the dosage of the first sulfate is 0.9-1.2 times of the theoretical dosage required by lithium reaction in the waste power battery raw material, and the dosage of the second sulfate is 0.05-0.2 times of the theoretical dosage required by lithium reaction in the waste power battery raw material;
(2) Carrying out water leaching on the calcine, and filtering to obtain nickel-cobalt-manganese slag and a lithium-rich solution;
(3) Acid leaching is carried out on the nickel-cobalt-manganese slag, and acid leaching solution is obtained through filtering;
(4) Performing displacement copper removal treatment on the pickle liquor, and filtering to obtain a copper-removed liquor;
(5) Carrying out high-temperature impurity removal and deep impurity removal on the copper-removed solution to obtain a nickel-containing cobalt manganese sulfate solution;
wherein the high-temperature impurity removal process comprises the following steps: in the presence of oxygen, adding sodium sulfate for impurity removal reaction, wherein the use amount of the sodium sulfate is 1/3-1 time of the molar amount of aluminum in the system solution according to molar amount, the pH value of the solution is controlled to be 1-3, the impurity removal reaction temperature is 180-250 ℃, and the impurity removal reaction time is 1-4h;
the process of deep impurity removal comprises the following steps: firstly, removing fluorine from the resin, and then neutralizing, precipitating and removing impurities.
2. The method of claim 1, wherein in step (1), the roasting conditions comprise: the roasting temperature is 500-1000 ℃, and the roasting time is 1-6 h;
and/or the waste power battery raw material comprises a positive electrode material.
3. The method according to claim 1, wherein in the step (2), the water immersion conditions comprise: the liquid-solid ratio is 2-10 mL/g, the water immersion temperature is 20-80 ℃, and the water immersion time is 0.5-2 h;
and/or, the step (2) further comprises the following steps: grinding the calcine before the water leaching, wherein the grinding enables the particle size of the calcine to be more than 200 meshes.
4. The method according to claim 1, wherein in step (3), the acid leaching process comprises: adding a sulfuric acid solution, wherein the amount of sulfuric acid in the sulfuric acid solution is 1-1.2 times of the theoretical amount of acid required by the reaction of the nickel-cobalt-manganese slag by mol, the liquid-solid ratio is 3-10 mL/g, then adding hydrogen peroxide for carrying out acid leaching reaction, wherein the acid leaching reaction temperature is 30-90 ℃, the acid leaching reaction time is 1-3h, and the end-point pH value is controlled to be 1.5-3; wherein the dosage of the hydrogen peroxide is 3-8vol.% of the system solution.
5. The method according to claim 1, wherein in the step (4), the process of the displacement copper removal treatment comprises: adding a copper removing agent for reaction at the temperature of 30-90 ℃ for 1-4h; wherein, the dosage of the copper removing agent is 1 to 2 times of the theoretical dosage required by the copper replacement reaction in the acid leaching solution, and the copper removing agent is at least one of iron powder, nickel powder and manganese powder.
6. The method according to claim 1, wherein in the high-temperature impurity removal in the step (5), the oxygen is introduced at a flow rate such that the oxygen pressure is maintained at 0.1-1 MPa;
and/or, the reaction temperature for removing impurities is 210-250 ℃;
the dosage of the sodium sulfate is 0.4 to 0.6 times of the molar weight of the aluminum in the system solution.
7. The method according to claim 1, wherein in the step (5), the resin defluorination process comprises: firstly, adding a pH regulator to control the pH value of the solution to be 3-5, and then introducing the solution into resin; wherein the resin is LX 760 or LX 860; the process of neutralizing, precipitating and removing impurities comprises the following steps: adding alkali liquor to control the pH value of the system to be 5.5-6.5.
8. The method of claim 1, further comprising the steps of:
(6) Purifying, neutralizing and precipitating the lithium-rich solution obtained in the step (2), and filtering to obtain purified lithium liquid and neutralized slag; using the purified lithium liquid to prepare battery-grade lithium carbonate; and (4) circulating the neutralized slag to the step (3) to be cooperated with the nickel-cobalt-manganese slag for acid leaching.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103789556A (en) * 2014-01-10 2014-05-14 中南大学 Method for recovering zinc in waste residue containing zinc ferrite through ferric sulfate roasting-water leaching
JP2016044319A (en) * 2014-08-21 2016-04-04 住友金属鉱山株式会社 Method for recovering valuable metal from waste nickel hydrogen battery
WO2018113477A1 (en) * 2016-12-23 2018-06-28 江西合纵锂业科技有限公司 Method for recovering cobalt and lithium from positive electrode material of spent lithium cobalt oxide battery
WO2020181745A1 (en) * 2019-03-12 2020-09-17 衢州华友钴新材料有限公司 Method for efficiently separating cobalt/nickel magnesium manganese from crude cobalt/nickel salt raw material
WO2022161086A1 (en) * 2021-01-29 2022-08-04 湖南邦普循环科技有限公司 Process for selectively recovering current collectors from spent lithium-ion batteries and application

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4892925B2 (en) * 2005-10-25 2012-03-07 住友金属鉱山株式会社 Method for recovering valuable metals from lithium-ion batteries
WO2007131278A1 (en) * 2006-05-15 2007-11-22 Orica Australia Pty Ltd Process for treatment of water to reduce fluoride levels
CN109935922B (en) * 2019-03-14 2020-11-27 北京矿冶科技集团有限公司 Method for recovering valuable metals from waste lithium ion battery materials
CN111825110A (en) * 2020-05-12 2020-10-27 宁夏百川新材料有限公司 Recycling method of waste lithium ion battery anode material
CN113073194B (en) * 2021-03-03 2022-09-09 安徽南都华铂新材料科技有限公司 Defluorination process for recycling waste lithium batteries

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103789556A (en) * 2014-01-10 2014-05-14 中南大学 Method for recovering zinc in waste residue containing zinc ferrite through ferric sulfate roasting-water leaching
JP2016044319A (en) * 2014-08-21 2016-04-04 住友金属鉱山株式会社 Method for recovering valuable metal from waste nickel hydrogen battery
WO2018113477A1 (en) * 2016-12-23 2018-06-28 江西合纵锂业科技有限公司 Method for recovering cobalt and lithium from positive electrode material of spent lithium cobalt oxide battery
WO2020181745A1 (en) * 2019-03-12 2020-09-17 衢州华友钴新材料有限公司 Method for efficiently separating cobalt/nickel magnesium manganese from crude cobalt/nickel salt raw material
WO2022161086A1 (en) * 2021-01-29 2022-08-04 湖南邦普循环科技有限公司 Process for selectively recovering current collectors from spent lithium-ion batteries and application

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