CN113921932A - Precursor solution, preparation method thereof, positive electrode material and lithium ion battery - Google Patents

Precursor solution, preparation method thereof, positive electrode material and lithium ion battery Download PDF

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CN113921932A
CN113921932A CN202111519497.4A CN202111519497A CN113921932A CN 113921932 A CN113921932 A CN 113921932A CN 202111519497 A CN202111519497 A CN 202111519497A CN 113921932 A CN113921932 A CN 113921932A
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solution
aluminum
copper
carbonate
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CN113921932B (en
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王海北
邓超群
李诗丽
李强
周起帆
秦树辰
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BGRIMM Technology Group Co Ltd
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    • H—ELECTRICITY
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22B23/04—Obtaining nickel or cobalt by wet processes
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    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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    • 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
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    • 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
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    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
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Abstract

The invention relates to the field of lithium ion battery recycling, in particular to a precursor solution and a preparation method thereof, a positive electrode material and a lithium ion battery. The preparation method of the precursor solution comprises the following steps: performing acid leaching treatment on the anode material of the waste lithium ion battery, and performing solid-liquid separation to obtain acid leaching solution; then mixing the pickle liquor with carbonate, carrying out solid-liquid separation after reaction, and preliminarily removing iron, aluminum and copper in the solution to obtain a first solution; and (3) removing fluorine from the first solution, mixing the first solution with alkali liquor, carrying out solid-liquid separation after reaction, and removing iron, aluminum and copper in the solution again to obtain a precursor solution. The method has the advantages that the impurity removal is performed by two steps through a neutralization precipitation method, the mixed material is adjusted to a specific pH value by respectively adopting carbonate and alkali liquor as neutralizing agents, the deep impurity removal of iron ions, aluminum ions and copper ions is realized, the process is simple, the operability is strong, the production cost is low, and the loss rate of nickel ions and/or cobalt ions and/or manganese ions in the impurity removal process is low.

Description

Precursor solution, preparation method thereof, positive electrode material and lithium ion battery
Technical Field
The invention relates to the field of lithium ion battery recycling, in particular to a precursor solution and a preparation method thereof, a positive electrode material and a lithium ion battery.
Background
With the market share of new energy vehicles becoming more and more new, the amount of waste power batteries is also increasing as the power batteries are one of the core components of new energy vehicles. The waste power battery contains a large amount of valuable metals, wherein the contents of Ni, Co, Mn and Li can respectively reach 5-12%, 5-20%, 7-10% and 2-5%. The recycling of the waste power batteries can not only improve the self-sufficiency of the raw materials, but also reduce the influence on the environment.
The method comprises the steps of recovering Ni, Co and Mn from the waste lithium battery anode material, mostly carrying out acid leaching and enrichment on the Ni, Co and Mn into acid leaching solution, then removing impurities by adopting methods such as chemical precipitation, replacement, ion exchange, extraction and the like, and separating and purifying the obtained impurity-removed solution to prepare various high-purity nickel-cobalt-manganese salts. For example, chinese patent CN112646974A discloses a method for recovering valuable metals from a positive electrode material of a waste ternary lithium battery, which comprises the steps of performing acid leaching on the positive electrode material to obtain an acid leaching solution, sequentially and respectively adding sodium carbonate and sodium fluoride to remove iron, aluminum, calcium, magnesium and lithium, and finally extracting cobalt, manganese and nickel by using P507 and P204. For another example, chinese patent CN110527835N discloses a method for recovering all components of a soft package of a waste ternary lithium battery, in which a sodium hydroxide solution is used to adjust the pH of an acid leaching solution to 6.5 ± 0.1, so as to remove impurities from Fe/Al, and then the solution after the impurities removal is directly precipitated to prepare a precursor. For another example, chinese patent CN112048615A discloses a method for recovering sulfate from waste ternary batteries, which comprises the steps of first roasting and separating aluminum foil and anode powder material from waste ternary batteries, then acid leaching the anode powder material, removing copper by extraction, neutralizing with sodium carbonate or sodium hydroxide to remove Fe/Al, and recovering nickel cobalt manganese sulfate by extraction and separation.
However, the above method has several problems: (1) the impurity removal or the separation of nickel, cobalt and manganese is realized by an extraction method, the extraction process is complicated, and the cost is high; (2) when the neutralization precipitation method is adopted for removing impurities, the used neutralizer is sodium hydroxide or sodium carbonate, and Ni/Co/Mn causes serious loss due to local over-alkali or generation of insoluble carbonate; (3) most of the prepared products are high-purity Ni/Co/Mn salt, and the high-purity Ni/Co/Mn salt is mixed when the precursor is prepared, so that the separation process is wasted, and the cost is increased.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of a precursor solution, which realizes deep impurity removal of iron, aluminum and copper ions by adopting a neutralization precipitation method for two-step impurity removal and respectively adopting carbonate and alkali liquor as neutralizers to adjust the mixed material to a specific pH value, has simple process flow, strong operability and low production cost without adopting an extraction method, has low loss rate of nickel and/or cobalt and/or manganese ions in the impurity removal process, and solves the problems of long impurity removal process flow, high cost, large wastewater discharge amount, serious loss of Ni, Co and Mn in the impurity removal process and the like in the prior art.
The second purpose of the invention is to provide a precursor solution, which can be directly used for preparing a precursor, has low cost and is beneficial to further popularization and use.
The third purpose of the invention is to provide a cathode material, the raw materials for preparing the cathode material are obtained from waste, the waste is changed into valuable, the environment is protected, and the cost is greatly saved.
The fourth purpose of the invention is to provide a lithium ion battery, which has low preparation cost.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a method of preparing a precursor solution, comprising the steps of:
(a) performing acid leaching treatment on the anode material of the waste lithium ion battery, and performing solid-liquid separation to obtain acid leaching solution; then mixing the pickle liquor with carbonate, carrying out solid-liquid separation after reaction, and preliminarily removing iron, aluminum and copper in the solution to obtain a first solution;
(b) removing fluorine from the first solution obtained in the step (a), mixing the first solution with alkali liquor, carrying out solid-liquid separation after reaction, and removing iron, aluminum and copper in the solution again to obtain a precursor solution;
in the step (a), in the reaction process of primarily removing iron, aluminum and copper in the solution, the pH value of the mixed material is 4.5-5.5;
in the step (b), in the reaction process of removing the iron, the aluminum and the copper in the solution again, the pH value of the mixed material is 6.2-6.8.
According to the preparation method of the precursor solution, the neutralization precipitation method is adopted to remove impurities in two steps, carbonate and alkali liquor are respectively adopted as neutralizing agents to adjust the mixed material to specific pH, so that deep impurity removal of iron, aluminum and copper ions is realized, the non-extraction method is adopted to enable the process flow to be simpler, the operability to be strong, the production cost to be low, the loss rate of nickel and/or cobalt and/or manganese ions in the impurity removal process to be low, and the problems that the impurity removal process flow is long, the cost is high, the waste water discharge amount is large, the Ni, Co and Mn loss in the impurity removal process is serious and the like in the prior art are solved.
Preferably, the positive electrode material of the waste lithium ion battery comprises at least one of a waste lithium nickelate positive electrode material, a waste lithium cobaltate positive electrode material, a waste lithium manganate positive electrode material, a waste nickel cobalt manganese ternary positive electrode material and a waste nickel cobalt aluminum ternary positive electrode material.
In some specific embodiments of the present invention, in step (a), during the reaction for primarily removing iron, aluminum and copper in the solution, the pH of the mixture may also be selected from 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3 and 5.4.
In some specific embodiments of the present invention, in step (b), during the reaction for removing iron, aluminum and copper in the solution again, the pH of the mixture may be selected to be 6.3, 6.4, 6.5, 6.6 or 6.7.
In some embodiments of the invention, in the step (a), the carbonate is dissolved in water to form a carbonate solution in suspension before the carbonate is added during the mixing of the pickle liquor and the carbonate. Preferably, the carbonate solution is 10-30% by mass, and can be selected from 12%, 15%, 18%, 20%, 23%, 25% or 28%.
The reaction principle of the preparation method of the precursor solution provided by the invention is as follows:
the method comprises the steps of carrying out acid leaching treatment on a positive electrode material of a waste lithium ion battery to obtain acid leaching solution, wherein the acid leaching solution comprises Ni, Co, Mn, Al, Fe, Cu and F plasmas, wherein Ni, Co and Mn are main metal elements of a lithium battery precursor, and Al, Fe, Cu and F are main impurity elements.
According to the invention, the neutralization precipitation method is adopted to realize the deep impurity removal of Al, Fe and Cu, the pH value of the mixed material is one of important factors influencing the impurity removal effect, the impurity removal of Al, Fe and Cu is more thorough when the pH value is larger, but the Ni, Co and Mn are seriously lost when the pH value is too large.
As shown in Table 1 below, the solubility product of each metal hydroxide in the pickle liquor at 25 ℃ is
Figure 370661DEST_PATH_IMAGE001
The value is obtained.
Figure 507245DEST_PATH_IMAGE002
Slightly soluble hydroxide M (OH)nThe quantitative relationship between the solubility and the pH is as follows:
Figure 176123DEST_PATH_IMAGE003
Figure 169487DEST_PATH_IMAGE004
metal hydroxide M (OH)nHas a solubility equal to the concentration of metal ions in the solutionC(M n+ ). Namely:
Figure 360035DEST_PATH_IMAGE005
Figure 97047DEST_PATH_IMAGE006
the metal ion concentrations can be calculated according to the formulas (1) to (4)C(M n+ ) Corresponding pH values from which the metal hydroxide M (OH) can be obtainednThe solubility s-pH chart of (A) is shown in FIG. 1. As can be seen from FIG. 1, the complete pH of Al and Fe precipitation is much lower than the pH at which Ni, Co and Mn begin to precipitate, and the complete pH of Cu precipitation is closer to the pH at which Ni, Co and Mn begin to precipitate.
In order to reduce the loss rate of Ni/Co/Mn in the impurity removal process, the two-stage method is adopted for impurity removal. In the first stage (namely the step (a)), the pH is controlled to be 4.5-5.5, so that a large amount of impurities of Fe and Al and a small amount of impurities of Cu are removed; meanwhile, part of F in the solution is also removed, which is mainly because when ferric hydroxide and aluminum hydroxide are generated and precipitated, the precipitate is partially hydrolyzed to generate alum floc, and fluoride is coagulated and adsorbed by the adsorption effect of the alum floc, so that part of F ions are removed.
And (c) in the second stage (namely the step (b)) controlling the pH to be 6.2-6.8, and realizing deep impurity removal of iron, aluminum and copper. As the alkalinity of the neutralizer alkali liquor used in the second-stage impurity removal process is higher, part of Ni and Co can be lost, the slag can be returned to the first-stage to be mixed with carbonate to be used as a neutralizer.
The precursor solution obtained after two-stage impurity removal can be used for preparing a precursor.
In step (b), the fluorine removal may be performed by any conventional fluorine removal method. Preferably, the method for removing fluorine comprises: a method for removing impurities of F by adding aluminum sulfate and strong alkali solution; or P507 is used as an extracting agent, Ni, Co and Mn are extracted to an organic phase, and fluorine is left in a water phase, so that the impurity removal of the fluorine is realized; or, a method of removing fluorine ions in the solution by adding a fluorine removing agent and diatomite; or adding a certain amount of solid cerium hydroxide, stirring at a certain temperature and pH, and standing to remove F ions.
Preferably, the mass concentration of fluoride ions in the solution after said defluorination is <10mg/L, more preferably <6 mg/L.
In some specific embodiments of the present invention, the method for removing fluorine comprises the following steps: and mixing the first solution, a flocculating agent and the carbonate solution, carrying out defluorination reaction, and carrying out solid-liquid separation after the reaction to obtain the defluorinated first solution.
The method for removing fluorine has high fluorine removal rate and low loss rate of Ni, Co and Mn.
Preferably, the flocculant comprises at least one of aluminum sulfate, aluminum chloride, aluminum nitrate, polyaluminum sulfate, and aluminum acetate.
Preferably, the mass fraction of the carbonate solution is 10% -30%, and 12%, 15%, 18%, 20%, 23%, 25% or 28% can be selected.
Preferably, in the mixed material after mixing, the molar ratio of the aluminum element in the flocculating agent to the fluorine element in the first solution is 2-6: 1.
Preferably, in the fluorine removal process, the pH of the mixed material is controlled to be 4.5-5.5, and 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3 or 5.4 can also be selected; the temperature of the mixed material is 40-60 ℃, and 42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃ or 58 ℃ can be selected; the reaction time is 0.5-2 h, and 1h or 1.5h can be selected.
By adopting specific temperature and reaction time, the F removing efficiency is improved.
Preferably, in step (a), the carbonate includes at least one of calcium carbonate, aluminum carbonate, nickel carbonate, cobalt carbonate, and manganese carbonate.
Preferably, in step (b), the alkali solution comprises sodium hydroxide solution and/or ammonia water.
Preferably, in the step (a), in the reaction process of primarily removing iron, aluminum and copper in the solution, the temperature of the mixed materials is 40-60 ℃, and 42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃ or 58 ℃ can be selected; the reaction time is 0.5-2 h, and 1h or 1.5h can be selected.
The impurity removal effect is improved by adopting specific temperature and reaction time.
Preferably, in step (a), the acid leaching treatment comprises a reduction acid leaching method and a roasting reduction acid leaching method.
Preferably, the reduction acid leaching method specifically comprises: and mixing the anode material of the waste lithium ion battery, a reducing agent and an acid solution for reaction.
Preferably, the roasting reduction acid leaching method specifically comprises: roasting the anode material of the waste lithium ion battery to obtain a roasted material; and then mixing the roasted material with a reducing agent and an acid solution for reaction.
Preferably, the roasting treatment includes one of carbothermic roasting, hydrogen reductive roasting, and acid roasting.
The carbon thermal reduction roasting realizes the cracking of the structure of the positive active material and the conversion of the nickel/cobalt/manganese higher oxide to the lower valence state metal or metal oxide by utilizing the reducibility of a carbon simple substance at a certain temperature.
The hydrogen reduction roasting realizes the cracking of the structure of the positive active material and the conversion of the nickel/cobalt/manganese higher oxide to the lower valence state metal or metal oxide by utilizing the reducibility of hydrogen at a certain temperature.
The acidizing roasting is to roast the anode active material structure at a certain temperature by adopting sulfuric acid or nitric acid to realize the sulfation/nitrification of the anode material nickel/cobalt/manganese/lithium.
More preferably, the reducing agent includes at least one of sodium sulfite, sodium thiosulfate, hydrogen peroxide, and hydrazine sulfate.
More preferably, the acid solution includes at least one of a hydrochloric acid solution, a sulfuric acid solution, a nitric acid solution, and an acetic acid solution.
In some embodiments of the invention, the sulfuric acid solution comprises concentrated sulfuric acid.
In some embodiments of the invention, the hydrochloric acid solution comprises concentrated hydrochloric acid.
More preferably, the acid used in the acid leach treatment has the same anion as the flocculant.
Preferably, in the step (b), in the reaction process of removing iron, aluminum and copper in the solution again, the temperature of the mixed materials is 30-90 ℃, and 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or 85 ℃ can be selected; the reaction time is 0.5-3 h, and 1h, 1.5h, 2h or 2.5h can be selected.
The adoption of specific temperature and reaction time is favorable for further improving the impurity removal effect.
The invention also provides a precursor solution prepared by the preparation method.
The precursor solution can be directly used for preparing a precursor, has low cost and is beneficial to further popularization and use.
The invention also provides a positive electrode material which is mainly prepared from the precursor solution prepared by the preparation method.
The preparation raw materials of the anode material are obtained from wastes, so that the waste is changed into valuable, the environment is protected, and the cost is greatly saved.
The invention also provides a lithium ion battery which comprises the cathode material.
The lithium ion battery has low preparation cost.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the preparation method of the precursor solution, provided by the invention, the neutralization precipitation method is adopted for removing impurities in two steps, and carbonate and alkali liquor are respectively adopted as neutralizing agents to adjust the mixed material to a specific pH value, so that the deep impurity removal of iron, aluminum and copper ions is realized, an extraction method is not adopted, the process flow is simpler, the operability is strong, the production cost is low, and the loss rate of nickel and/or cobalt and/or manganese ions in the impurity removal process is low.
(2) According to the preparation method of the precursor solution, the first solution is subjected to fluorine removal and then mixed with the alkali liquor, so that deep removal of fluorine is realized while deep removal of impurities of iron ions, aluminum ions and copper ions is realized, and the contents of Fe, Al, Cu and F in the prepared precursor solution are respectively reduced to about 0.001mg/L, about 0.01mg/L, about 0.001mg/L and about 3 mg/L.
(3) The precursor solution provided by the invention can be directly used for preparing a precursor, is low in cost and is beneficial to further popularization and use.
(4) The preparation raw materials of the anode material provided by the invention are obtained from wastes, so that the waste is changed into valuable, the environment is protected, and the cost is greatly saved.
(5) The lithium ion battery provided by the invention has low preparation cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 shows a sparingly soluble metal hydroxide M (OH) according to the present inventionns-pH profile of (a);
fig. 2 is a schematic flow chart of a method for preparing a precursor solution according to embodiment 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
FIG. 1 shows a sparingly soluble metal hydroxide M (OH) according to the present inventionns-pH profile of (A).
Example 1
The preparation method of the precursor solution provided in this embodiment is shown in fig. 2, and specifically includes the following steps:
(a) LiNi which is a nickel-cobalt-manganese ternary positive electrode material of waste lithium ion batteriesxCoyMnzO2Adopting reduction acid leaching method to perform acid leaching treatment, taking concentrated sulfuric acid as acid solution, H2O2As a reducing agent, filtering to obtain a leaching solution;
(b) taking 500mL of the leaching solution, and slowly adding 20 mass percent of MnCO into the leaching solution3And (3) regulating the pH value of the mixed material to 5, reacting at 55 ℃ for 1h, preliminarily removing iron, aluminum and copper in the solution, and performing solid-liquid separation after reaction to obtain 498mL of first solution.
(c) Taking 250mL of the first solution and 1.84g of Al2(SO4)3∙18H2O mixed with Al2(SO4)3∙18H2The molar ratio of the aluminum element in the O to the fluorine element in the first solution is 4:1, deep flocculation precipitation is carried out to remove fluorine, and after the mixture is stirred uniformly, 20 mass percent of MnCO is added into the mixture3The solution was adjusted to pH 5, reacted at 55 ℃ for 1h, and filtered to obtain 248mL of a solution after defluorination.
(d) And taking 200mL of the solution after defluorination, adding 0.01mol/L NaOH solution into the solution, adjusting the pH value of the mixed material to be 6.5, reacting at 70 ℃ for 1h, removing iron, aluminum and copper in the solution again, and filtering to obtain 193mL of precursor solution.
Wherein, the contents of each element in the leaching solution, the first solution, the solution after fluorine removal and the precursor solution are shown in the following table 2.
TABLE 2 contents of the elements in the leach solution, the first solution, the solution after defluorination and the precursor solution
Figure 620432DEST_PATH_IMAGE007
As is clear from Table 2, the contents of Fe, Al, Cu and F were reduced to 0.001mg/L, 0.02mg/L, 0.001mg/L and 3.23mg/L, respectively, and the loss rates of Ni, Co and Mn were all 0.05% or less in the processes except for Fe, Al, Cu and F. The slag contains Ni, Co and Mn below 0.05%, and has no values of recovering Ni, Co and Mn.
Example 2
The preparation method of the precursor solution provided by the embodiment comprises the following steps:
(a) LiNi which is a nickel-cobalt-manganese ternary positive electrode material of waste lithium ion batteriesxCoyMnzO2Carrying out acid leaching treatment by adopting a roasting reduction acid leaching method, and firstly carrying out carbothermic reduction roasting on the nickel-cobalt-manganese ternary positive electrode material to obtain a roasted material; then concentrated hydrochloric acid as acid solution, H2O2As a reducing agent, filtering to obtain a leaching solution;
(b) 500mL of the leaching solution is taken, and NiCO with the mass fraction of 10 percent is slowly added into the leaching solution3And (3) regulating the pH value of the mixed material to be 4.5, reacting at 60 ℃ for 0.5h, preliminarily removing iron, aluminum and copper in the solution, and carrying out solid-liquid separation after reaction to obtain 502mL of first solution.
(c) Taking 250mL of the first solution and 0.43g of AlCl3Mixing in which AlCl is3The molar ratio of the aluminum element in the solution to the fluorine element in the first solution is 2:1, deep flocculation precipitation is carried out to remove fluorine, after uniform stirring, NiCO with the mass fraction of 10 percent is added into the solution3The solution, pH adjusted to 4.5, was then reacted at 60 ℃ for 0.5h and filtered to give 253mL of defluorinatedAnd (5) post-treating.
(d) And taking 200mL of the defluorinated solution, adding 0.1mol/L ammonia water into the defluorinated solution, adjusting the pH of the mixed material to be 6.2, reacting at 30 ℃ for 3 hours, removing iron, aluminum and copper in the solution again, and filtering to obtain 208mL of precursor solution.
The contents of the elements in the leaching solution, the first solution, the solution after fluorine removal and the precursor solution are shown in table 3 below.
TABLE 3 contents of the respective elements in the leach liquor, the first solution, the post-fluorine removal liquor and the precursor solution
Figure 987959DEST_PATH_IMAGE008
As is clear from Table 3, the contents of Fe, Al, Cu and F were reduced to 0.001mg/L, 0.01mg/L, 0.001mg/L and 3.54mg/L, respectively, and the loss rates of Ni, Co and Mn were all 0.05% or less in the processes except for Fe, Al, Cu and F. The slag contains Ni, Co and Mn below 0.05%, and has no values of recovering Ni, Co and Mn.
Example 3
The preparation method of the precursor solution provided by the embodiment comprises the following steps:
(a) carrying out acid leaching treatment on the waste lithium cobaltate positive electrode material by adopting a roasting reduction acid leaching method, and firstly carrying out hydrogen reduction roasting on the nickel-cobalt-manganese ternary positive electrode material to obtain a roasted material; then concentrated hydrochloric acid as acid solution, H2O2As a reducing agent, filtering to obtain a leaching solution;
(b) taking 500mL of the leaching solution, and slowly adding 30% of CoCO by mass fraction into the leaching solution3And (3) adjusting the pH value of the mixed material to 5.5, reacting at 40 ℃ for 2h, preliminarily removing iron, aluminum and copper in the solution, and carrying out solid-liquid separation after reaction to obtain 508mL of first solution.
(c) Taking 250mL of the first solution and 1.38g of AlCl3Mixing in which AlCl is3The molar ratio of the aluminum element in the solution to the fluorine element in the first solution is 6:1, deep flocculation precipitation is carried out to remove fluorine, and after uniform stirring, CoCO with the mass fraction of 30 percent is added into the solution3Solution, adjusting pH to 5.2, thenReact for 1.5h at 55 ℃ and are filtered to obtain 256mL of liquid after defluorination.
(d) And taking 200mL of the solution after defluorination, adding 0.01mol/L of sodium hydroxide solution into the solution, adjusting the pH of the mixed material to be 6.8, reacting at 85 ℃ for 0.5h, removing iron, aluminum and copper in the solution again, and filtering to obtain 189mL of precursor solution.
The contents of the elements in the leaching solution, the first solution, the solution after fluorine removal and the precursor solution are shown in table 4 below.
TABLE 4 contents of the elements in the leach solution, the first solution, the post-fluorine removal solution and the precursor solution
Figure 229585DEST_PATH_IMAGE009
As can be seen from Table 4, the contents of Fe, Al, Cu and F were reduced to 0.001mg/L, 0.006mg/L, 0.001mg/L and 1.35mg/L, respectively, and the loss rate of Co in the process of removing Fe, Al, Cu and F was 0.03% or less. The Co content in the slag is below 0.04 percent, and the value of recovering Ni, Co and Mn is not possessed.
Example 4
The preparation method of the precursor solution provided by the embodiment comprises the following steps:
(a) LiNi which is a nickel-cobalt-manganese ternary positive electrode material of waste lithium ion batteriesxCoyMnzO2Adopting reduction acid leaching method to perform acid leaching treatment, taking concentrated sulfuric acid as acid solution, H2O2As a reducing agent, filtering to obtain a leaching solution;
(b) and (3) taking 500mL of the leaching solution, slowly adding aluminum carbonate solid powder into the leaching solution, adjusting the pH value of the mixed material to be 4.8, reacting at 45 ℃ for 1.5h, preliminarily removing iron, aluminum and copper in the solution, and carrying out solid-liquid separation after reaction to obtain 490mL of first solution.
(c) Taking 250mL of the first solution and 1.38g of Al2(SO4)3∙18H2O mixed with Al2(SO4)3∙18H2The molar ratio of the aluminum element in the O to the fluorine element in the first solution is 4:1, deep flocculation precipitation is carried out to remove fluorine, and stirring is carried outAfter homogenization, aluminum carbonate powder was slowly added thereto to adjust the pH to 5.0, followed by reaction at 45 ℃ for 1.5 hours, and filtration to obtain 240mL of a post-defluorination solution.
(d) And mixing 200mL of the defluorinated solution with 0.2mol/L ammonia water, adjusting the pH of the mixed material to 6.4, reacting at 45 ℃ for 2.5 hours, removing iron, aluminum and copper in the solution again, and filtering to obtain 204mL of precursor solution.
The contents of the elements in the leaching solution, the first solution, the solution after fluorine removal and the precursor solution are shown in table 5 below.
TABLE 5 contents of the respective elements in the leach liquor, the first solution, the post-fluorine removal liquor and the precursor solution
Figure 504708DEST_PATH_IMAGE010
As is clear from Table 5, the contents of Fe, Al, Cu and F were reduced to 0.001mg/L, 0.006mg/L, 0.001mg/L and 0.47mg/L, respectively, and the loss rates of Ni, Co and Mn were all 0.03% or less in the processes except for Fe, Al, Cu and F. The slag contains Ni, Co and Mn below 0.04%, and has no values of recovering Ni, Co and Mn.
Comparative example 1
The preparation method of the precursor solution provided by the comparative example comprises the following steps:
(a) 500mL of the leachate prepared in the step (a) in example 1 is taken, a 20% sodium hydroxide solution is added to the leachate, the pH value of the mixed material is adjusted to 5, the mixed material is reacted for 1h at 55 ℃, iron, aluminum and copper in the solution are primarily removed, and after the reaction, solid-liquid separation is carried out, so that 504mL of a first solution is obtained.
(b) Taking 250mL of the first solution and 1.38g of Al2(SO4)3∙18H2O mixed with Al2(SO4)3∙18H2The molar ratio of the aluminum element in the O to the fluorine element in the first solution is 4:1, deep flocculation precipitation is carried out for removing fluorine, after uniform stirring, a sodium hydroxide solution with the mass fraction of 20% is slowly added into the solution, the pH value is adjusted to 5.0, then the reaction is carried out for 1.5h at the temperature of 45 ℃, and the solution is filtered to obtain 238mL of liquid after fluorine removal.
(c) This step was substantially the same as the step (d) in example 1 except that the volume of the precursor solution was different, and 194mL of the precursor solution was obtained in this comparative example.
The contents of the elements in the leaching solution, the first solution, the solution after fluorine removal and the precursor solution are shown in table 6 below.
TABLE 6 contents of the respective elements in the leach liquor, the first solution, the post-fluorine removal liquor and the precursor solution
Figure 85862DEST_PATH_IMAGE011
As is clear from Table 6, the contents of Fe, Al, Cu and F in the precursor solution were 0.001mg/L, 0.04mg/L, 0.001mg/L and 2.73mg/L, respectively. In the processes of removing Fe, Al, Cu and F, the loss rates of Ni, Co and Mn were 26.13%, 18.60% and 9.67%, respectively, and it was found that this method resulted in severe loss of nickel, cobalt and manganese ions.
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that the above embodiments are merely illustrative of the technical solution of the present invention and are not restrictive; those of ordinary skill in the art will understand that: modifications may be made to the above-described embodiments, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the present invention; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; it is therefore intended to cover in the appended claims all such alternatives and modifications that are within the scope of the invention.

Claims (10)

1. A method for preparing a precursor solution is characterized by comprising the following steps:
(a) performing acid leaching treatment on the anode material of the waste lithium ion battery, and performing solid-liquid separation to obtain acid leaching solution; then mixing the pickle liquor with carbonate, carrying out solid-liquid separation after reaction, and preliminarily removing iron, aluminum and copper in the solution to obtain a first solution;
(b) removing fluorine from the first solution obtained in the step (a), mixing the first solution with alkali liquor, carrying out solid-liquid separation after reaction, and removing iron, aluminum and copper in the solution again to obtain a precursor solution;
in the step (a), in the reaction process of primarily removing iron, aluminum and copper in the solution, the pH value of the mixed material is 4.5-5.5;
in the step (b), in the reaction process of removing the iron, the aluminum and the copper in the solution again, the pH value of the mixed material is 6.2-6.8.
2. The method according to claim 1, wherein in step (a), the carbonate comprises at least one of calcium carbonate, aluminum carbonate, nickel carbonate, cobalt carbonate, and manganese carbonate.
3. The method according to claim 1, wherein in the step (b), the alkali solution comprises a sodium hydroxide solution and/or ammonia water.
4. The preparation method according to any one of claims 1 to 3, wherein in the step (a), in the reaction process of primarily removing iron, aluminum and copper in the solution, the temperature of the mixed materials is 40 to 60 ℃, and the reaction time is 0.5 to 2 hours.
5. The method according to any one of claims 1 to 3, wherein in the step (a), the temperature of the mixture is 45 to 55 ℃ during the reaction for primarily removing iron, aluminum and copper in the solution.
6. The method according to any one of claims 1 to 3, wherein in the step (a), the acid leaching treatment includes a reduction acid leaching method and a roasting reduction acid leaching method.
7. The method according to any one of claims 1 to 3, wherein in the step (b), the temperature of the mixture is 30 to 90 ℃ and the reaction time is 0.5 to 3 hours in the reaction process of removing iron, aluminum and copper in the solution again.
8. A precursor solution obtained by the production method according to any one of claims 1 to 7.
9. A positive electrode material mainly prepared from the precursor solution prepared by the preparation method of any one of claims 1 to 7.
10. A lithium ion battery comprising the positive electrode material of claim 9.
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