CN113548701A - Preparation and application method of lithium ion sieve - Google Patents

Preparation and application method of lithium ion sieve Download PDF

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CN113548701A
CN113548701A CN202110903980.6A CN202110903980A CN113548701A CN 113548701 A CN113548701 A CN 113548701A CN 202110903980 A CN202110903980 A CN 202110903980A CN 113548701 A CN113548701 A CN 113548701A
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manganese
lithium ion
lithium
solution
leaching
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周蕾
袁永顺
葛梦丹
李璐
赵燕禹
于韶梅
王雪
刘炳光
李建生
王晨
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Tianjin Vocational Institute
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • 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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Abstract

The invention relates to a method for preparing an aluminum, cobalt and nickel co-doped manganese lithium ion sieve by taking a waste ternary lithium ion battery anode material as a raw material. Reducing and dissolving the anode material of the waste ternary lithium ion battery in a hydrochloric acid aqueous solution by aluminum powder to form an aqueous solution of cobalt-nickel-manganese-aluminum chloride; oxidizing with sodium chloride solution to produce manganese dioxide precipitate; neutralizing with sodium hydroxide solution to generate LiCl2﹒2Al(OH)3Precipitating the double salt; uniformly mixing the two precipitates, and then roasting at high temperature to form a manganese-doped lithium ion sieve precursor; the manganese-doped lithium ion sieve is prepared by removing lithium with dilute hydrochloric acid, and the chemical composition of the manganese-doped lithium ion sieve is H1.33CoxNiyAlzMn1.67‑x‑y‑zO4﹒nAl2O3Wherein x =0.005-0.05, y =0.005-0.05, z =0.005-0.05, n = 1.3-2.5; the lithium adsorption capacity of the lithium ion battery is 15-21mg/g measured in 0.5g/L lithium chloride aqueous solution, the manganese dissolution rate after 10 times of adsorption and desorption is 0.8% -1%, and the lithium ion battery can be applied to adsorption and separation of lithium salts in the reduction leaching solution of the waste ternary lithium ion battery anode material.

Description

Preparation and application method of lithium ion sieve
Technical Field
The invention relates to a preparation and application method of a lithium ion sieve, in particular to a method for preparing an aluminum, cobalt and nickel co-doped manganese lithium ion sieve by taking a waste ternary lithium ion battery anode material as a raw material and adsorbing and separating lithium salt in a reduction leaching solution of the waste ternary lithium ion battery anode material, belonging to the field of chemical industry and new energy materials.
Technical Field
After the lithium ion battery is repeatedly charged and discharged, the electrode material is separated from the current collector through repeated expansion and contraction, so that poor contact is caused; in addition, the dendritic crystal of the crystal form of the anode material grows up in the repeated charging and discharging process, so that lithium ions cannot be freely inserted and removed in the crystal structure, and the capacity is greatly attenuated, so that the lithium ion battery needs to be reprocessed after the material is recovered after the lithium ion battery is used for 3-5 years. The lithium ion battery comprises 25% of a positive electrode, 30% of a negative electrode, 15% of electrolyte, 4% of a diaphragm and 26% of a package by mass. The cost of the anode material in the lithium ion battery is the highest, so the recycling of the waste lithium ion battery is mainly the recycling of the anode material.
The ternary lithium ion battery refers to a lithium nickel cobalt manganese oxide (LiNi) as a positive electrode materialxCoyMn1-x-yO2) Or lithium nickel cobalt aluminate (LiNi)xCoyAl1-x-yO2) The lithium ion battery of (1). The ternary lithium ion battery is a mainstream variety in the current lithium ion battery market, and the recovery amount of the ternary lithium ion battery accounts for 68%, the recovery amount of the lithium iron phosphate battery accounts for 26%, and other types of lithium ions account for 26% in 2025 yearsThe battery is about 6%. The recycling of ternary lithium ion batteries is the key point of enterprise layout, and 200 million yuan of market space exists every year. The ternary lithium ion battery anode material is produced by taking nickel salt, cobalt salt, manganese salt and lithium salt as raw materials, and the proportion of nickel, cobalt and manganese in the ternary lithium ion battery anode material can be adjusted according to actual needs. Commercially available ternary lithium ion batteries mainly have models of NCM111, NCM523, NCM622, and NCM811, depending on the molar ratio of Ni, Co, and Mn in the positive electrode material. The mass composition of the valuable metals in the anode material is generally Ni 10-20%, Co 5-10%, Mn 10-15% and Li 2-6%. Because of the low price of manganese, the manganese content in the non-brand cathode material is higher than the specified content.
The positive electrode material of the ternary lithium ion battery comprises 50-58% of valuable metal by mass, 86-100% of nickel cobalt lithium manganate by mass, and a small amount of conductive carbon material and polymer adhesive. Different from experimental materials of self-separated waste ternary lithium ion batteries, aluminum, copper and iron metal materials introduced during mechanical crushing processing are added in recovered anode materials of commercial waste ternary lithium ion batteries, and the mass compositions of the valuable metals are generally Ni 15-20%, Co 15-18%, Mn 8-12%, Li 4-6% and Al 2-10%. Aluminum is derived from the aluminum collector foil and the battery aluminum case, copper is derived from the negative collector, and iron is derived from the battery case and the wear of the recycling crushing equipment. The copper-aluminum-iron metal can be roughly separated from the nickel-cobalt lithium manganate through specific gravity difference and a mechanical mode. Wherein, the mass of the recoverable aluminum foil accounts for 17.2% of the mass of the waste lithium ion battery, and the mass of the recoverable aluminum shell accounts for 15.8% of the mass of the waste lithium ion battery.
The large-scale recovery process of the waste ternary lithium ion battery is very complex, the lithium recovery rate is required to be more than 85% and the nickel-cobalt-manganese recovery rate is required to be more than 98% in the new specification of the waste power lithium ion industry, so that the problems of lithium resource waste and heavy metal manganese pollution caused by the fact that some waste lithium ion battery recycling enterprises only pursue short-term economic benefits and do not pay attention to lithium-manganese resource recovery are solved. If the valuable metal recovery of the waste lithium ion battery is combined with the preparation of the manganese lithium ion sieve, the valuable metal wet recovery process in the waste ternary lithium ion battery is simplified.
The lithium ion sieve is prepared by introducing template Li into inorganic compound+First, a lithium ion sieve precursor is formed, and then Li in the lithium ion sieve precursor is added+And forming the lithium ion sieve adsorbent after extraction. According to the memory effect, size effect and sieving effect of molecules, the lithium ion sieve adsorbent can be used for Li under the condition of coexistence of multiple ions+Ions have high adsorption selectivity, so that Li is adsorbed+The ions are separated from other ions, and the method is particularly suitable for separating Li from lithium-containing dilute solutions such as waste lithium battery material leaching solution, lithium salt production waste liquid, salt lake brine and the like+Selective adsorption separation.
If the manganese salt recovered from the waste ternary lithium ion battery is recycled for producing the lithium ion battery material, the aluminum impurities in the manganese salt are required to be separated and removed completely. If the recovered manganese salt is used for preparing a manganese-based lithium ion sieve for selectively extracting lithium from a low-concentration lithium-containing aqueous solution, aluminum impurities are a beneficial component, and separation and removal are not necessary. For example, chinese patent CN109529757B (2020-10-23) discloses a method for preparing a surface-doped long-life lithium ion sieve adsorbent, which reduces the manganese dissolution loss rate and prolongs the service life by doping and coating a manganese-based lithium ion sieve with alumina. Chinese patent CN110013822B (2020-02-14) discloses a method for recovering waste lithium ion batteries and co-producing lithium adsorbent, and the precursor composition is Li1.6Mn1.6O4Allowing 2% -6% Co impurity to be present therein to simplify the separation process. Chinese patent CN103045870B (2014-03-26) discloses a method for comprehensively recovering valuable metals of waste lithium ion batteries and preparing manganese lithium ion sieves, which is used for recovering and processing lithium ion battery materials.
The waste ternary lithium ion battery material is recycled by a wet method, and the problem of dissolution or leaching of the nickel cobalt lithium manganate cathode material is solved. The nickel cobalt lithium manganate is a solid solution of high-valence nickel cobalt manganese oxide, and is difficult to dissolve or leach in an acid-base aqueous solution without a reducing agent. The patent discloses that various inorganic and organic reducing agents are used for reduction leaching of waste ternary lithium ion battery anode materials, and the classical method adopts the mixed solution of dilute sulfuric acid and hydrogen peroxide for dissolution or leaching, and the hydrogen peroxide is used as a reducing agent. In order to improve the leaching rate of metals in the positive electrode material, the positive electrode material is generally subjected to high-temperature heat treatment, a polymer binder in the positive electrode material is thermally decomposed, and then the positive electrode material adhered to the surface of the collector is separated and is convenient to leach by adopting a mode of dissolving the surface of an aluminum foil under an alkaline condition.
Disclosure of Invention
The invention aims to provide a preparation method of a lithium ion sieve, in particular to a method for preparing an aluminum, cobalt and nickel co-doped manganese series lithium ion sieve by taking a waste ternary lithium ion battery anode material as a raw material, which ensures that the recovery rate of lithium and manganese components with high recovery difficulty reaches 85 percent and 98 percent of the requirement of the industry standard so as to improve the economic benefit and solve the problem of heavy metal manganese pollution, and the technical scheme comprises four parts of reduction leaching of the anode material, separation of manganese salt in leaching solution, separation of lithium salt in the leaching solution and preparation of the manganese series lithium ion sieve:
(1) the reduction leaching of the anode material is to add commercial waste ternary lithium ion battery anode material powder with valuable metals of which the mass components are Ni 15-20%, Co 15-18%, Mn 10-18%, Li 4-8% and Al 4-10% into 0.5-1.0mol/L hydrochloric acid aqueous solution under stirring in batches, react aluminum in the anode material powder with hydrochloric acid to generate aluminum chloride, reduce high-valence-state nickel cobalt lithium manganate into cobalt chloride, nickel chloride, manganese chloride and lithium chloride under an acidic condition, replenish an aluminum powder reducing agent at the leaching solution temperature of 60-90 ℃, and control the Al/Mn molar ratio in the leaching solution to be 1.7-3: 1, completely reducing and leaching the anode material; replenishing hydrochloric acid aqueous solution, controlling the concentration of hydrochloric acid to be 0.5-1.0mol/L, and completing the reduction leaching process within 4-12 h; filtering and separating insoluble residues in the leaching solution to ensure that the leaching rate of valuable metals reaches 98-100 percent;
(2) separating manganese salt in the leaching solution by adding a sodium chlorate solution into the leaching solution in batches, controlling the temperature of the leaching solution to be 60-90 ℃, controlling the molar ratio of sodium chlorate to manganese to be 0.5-0.6:1, and completely oxidizing manganese chloride in the leaching solution into manganese dioxide precipitate; controlling the concentration of hydrochloric acid in the leaching solution to be 0.3-0.7mol/L so as to avoid the release of a large amount of chlorine and the reduction and dissolution of manganese dioxide by hydrochloric acid in the oxidation process; filtering the generated manganese dioxide precipitate, and washing with deionized water to remove salt carried by the manganese dioxide;
(3) in the leaching solutionThe lithium salt separation is to add sodium hydroxide solution into the leaching solution to neutralize the leaching solution to pH6-8, only aluminum hydroxide can form precipitate at the moment, and the aluminum hydroxide can selectively adsorb lithium chloride in the leaching solution to generate LiCl2﹒2Al(OH)3Precipitating the double salt; cobalt salt and nickel salt are adsorbed in the aluminum hydroxide precipitation process; the LiCl produced was separated by filtration2﹒2Al(OH)3Precipitating the double salt, and washing with deionized water to remove the salt carried by the double salt;
(4) the manganese-based lithium ion sieve is prepared by filtering and separating the above manganese dioxide precipitate and LiCl2﹒2Al(OH)3Mixing and grinding the double salt precipitate, controlling the molar ratio of Li/Mn in the mixture to be 0.85-1.0, drying at the temperature of 110-; soaking and delithiating with 0.5mol/L hydrochloric acid, washing the salt content with deionized water, and drying at 110-130 ℃ to obtain the aluminum, cobalt and nickel co-doped manganese lithium ion sieve with the chemical composition of H1.33CoxNiyAlzMn1.67-x-y-zO4﹒nAl2O3Wherein x =0.01-0.05, y =0.01-0.05, z =0.01-0.05, n = 1.3-2.5; the lithium adsorption capacity of the lithium ion battery is 15-21mg/g measured in 0.5g/L lithium chloride aqueous solution, and the manganese dissolution rate is 0.8% -1% after 10 times of adsorption and desorption.
In the existing recycling of waste ternary lithium ion battery materials, aluminum components in the waste ternary lithium ion battery materials are thoroughly removed. For the preparation of the manganese-based lithium ion sieve, the aluminum salt is also a lithium ion sieve with low adsorption capacity, can improve the selectivity of the manganese-based lithium ion sieve, and can play the following 4 roles: (1) the alumina formed in situ is used as a carrier, so that the manganese lithium ion sieve can be directly sintered and processed into various types of fillers, and is conveniently applied to adsorption and desorption of industrial adsorption columns; (2) the in-situ formed alumina is used as a carrier, so that the surface area of the manganese lithium ion sieve is enlarged, the absorption and desorption speed of lithium ions is increased, and the absorption and desorption balance time is shortened; (3) the aluminum oxide formed in situ is coated on the surface of the manganese-based lithium ion sieve, so that the manganese-based lithium ion sieve can resist acid dissolution to a certain extent, and the dissolution loss rate of the manganese-based lithium ion sieve is reduced; (4) the aluminum is doped into the molecular structure of the manganese-based lithium ion sieve, so that unstable trivalent manganese is replaced, the stability of the manganese-based lithium ion sieve is improved, the molecular structure can be kept intact after lithium removal, and the cycle service life can be prolonged.
The manganese-based lithium ion sieve precursor with a spinel structure comprises LiMn2O4、Li1.33Mn1.67O4And Li1.67Mn1.67O4In various forms, the Li/Mn ratios are 0.5, 0.8 and 1.0, respectively. With the increase of the Li/Mn ratio, the theoretical adsorption capacity of the lithium ion sieve is increased to 38mg/g, 56mg/g and 68mg/g respectively, but the stability of the molecular structure is reduced, so that unstable trivalent manganese in the manganese lithium ion sieve is easy to generate disproportionation reaction, and the dissolution loss of manganese during acid washing is increased. A small amount of aluminum, cobalt or nickel is doped into the molecular structure of the manganese-based lithium ion sieve to replace unstable trivalent manganese, so that the stability of the spinel structure can be improved, and the dissolution loss rate of manganese in the acid washing regeneration process is reduced. In the invention, the aluminum, cobalt or nickel doping elements are native in the anode material of the waste ternary lithium ion battery and are residual in the separation process, and for the preparation of the manganese lithium ion sieve, the aluminum, the cobalt and the nickel are beneficial impurities.
The invention also aims to provide an application method of the lithium ion sieve, in particular to an aluminum, cobalt and nickel co-doped manganese lithium ion sieve prepared by using the anode material of the waste ternary lithium ion battery as the raw material, and a method for selectively adsorbing and extracting lithium from the leaching solution of the anode material of the waste ternary lithium ion battery, wherein the lithium salt is firstly selectively adsorbed and separated, so that the entrainment loss during the separation of cobalt, nickel and manganese is avoided, and the high recovery rate of lithium is ensured, so that other valuable metals of cobalt, nickel and manganese can be efficiently separated according to the traditional precipitation method or extraction method, and the 98% recovery rate required by the industry specification is achieved, so that the economic benefit is improved and the heavy metal pollution problem is solved, and the technical scheme comprises five parts of reduction leaching of the anode material, selective adsorption separation of the lithium salt, regeneration of the lithium ion sieve, preparation of lithium carbonate and separation of cobalt, nickel and manganese compounds:
(1) the reduction leaching of the anode material is to leach the anode material after carbothermic reduction, catalytic reduction and chemical reduction with an aqueous solution, or to neutralize the anode material to the pH of 6-8 after leaching with an aqueous solution of sulfuric acid, hydrochloric acid or nitric acid, and to filter insoluble residues, wherein the composition of an impurity removal leaching solution is as follows: ni10-19 g/L, Co15-19 g/L, Mn8-19 g/L, Li2-9g/L, Al2-9 g/L;
(2) the lithium salt selective adsorption separation is to pass the impurity-removed leaching solution through a lithium ion sieve packing column to ensure that lithium ions in the leaching solution are selectively adsorbed by the manganese-doped lithium ion sieve, control the flow rate of the leaching solution to ensure that the lithium ion sieve reaches saturated adsorption for 4-12h, and then wash the manganese-doped lithium ion sieve by water to remove cobalt, nickel and manganese salt attached to the surface of the manganese-doped lithium ion sieve;
(3) the regeneration of the lithium ion sieve is to slowly drip and wash the saturated and adsorbed manganese-doped lithium ion sieve by 0.5mol/L hydrochloric acid solution, the desorption rate of the lithium ions reaches 90 to 98 percent, the manganese-doped lithium ion sieve is washed by water and enters the next lithium adsorption cycle for 10 times of adsorption and desorption cycles, and the manganese dissolution loss rate of the manganese-doped lithium ion sieve is 0.8 to 1 percent;
(4) the preparation of lithium carbonate is to concentrate eluent doped with manganese lithium ion sieve, add sodium carbonate solution to adjust the pH of the solution to 11, filter the precipitated cobalt, nickel and manganese impurities and obtain refined lithium carbonate solution; adding excessive sodium carbonate solution to adjust the pH value of the solution to 14 so as to convert lithium chloride in the solution into insoluble lithium carbonate precipitate; filtering, washing and drying the lithium carbonate precipitate to obtain a battery-grade lithium carbonate product, wherein the mother liquor can be recycled to ensure that the recovery rate of lithium in the leaching solution reaches 95-99%;
(5) the separation of cobalt-nickel-manganese compound is that one of sodium oxalate saturated solution, sodium carbonate solution or sodium hydroxide solution is added into leaching solution from which lithium salt is separated, so that cobalt-nickel-manganese salt in the leaching solution generates one of oxalate precipitate, carbonate precipitate or hydroxide precipitate, the precipitate is filtered and separated, washed and dried to obtain cobalt-nickel-manganese insoluble compound, which is used as raw material for preparing ternary lithium ion battery material again, and the mother solution is recycled for wastewater treatment.
The experimental raw material anode material of the waste ternary lithium ion battery is obtained from an industrial product purchased on the internet or a self-disassembled ternary lithium battery, and the aluminum powder, the sodium chlorate, the hydrochloric acid and the lithium chloride are all commercially available chemical pure reagents.
The invention has the beneficial effects that:
(1) the preparation of the manganese-based lithium ion sieve is combined with the recovery of valuable metals of the waste ternary lithium ion battery, so that the wet recovery process of the valuable metals in the waste ternary lithium ion battery is simplified;
(2) aluminum impurities in the waste ternary lithium ion battery material are used as the reducing agent for reducing and leaching the anode material and the components of the manganese lithium ion sieve, so that the separation process is simplified, and comprehensive utilization is realized;
(3) the manganese-doped lithium ion sieve is adopted to extract lithium from the leaching solution of the anode material of the waste ternary lithium ion battery, and lithium salt is firstly absorbed and separated, so that the high recovery rate of the lithium is ensured.
Detailed Description
Example 1
Weighing 104.3g of recovered powder of the anode material of the waste NCM111 type ternary lithium ion battery, wherein the mass composition of the recovered powder is as follows: ni18.7%, Co18.7%, Mn17.4%, Li6.7% and Al7.7%. Adding 1.0mol/L hydrochloric acid aqueous solution 3.9L in batches under stirring, reacting aluminum in the positive electrode material powder with hydrochloric acid to generate aluminum chloride, reducing high-valence-state nickel-cobalt lithium manganate into cobalt chloride, nickel chloride, manganese chloride and lithium chloride under an acidic condition, and cooling the leaching solution to 90 ℃. Replenishing 9.7 g of aluminum powder reducing agent, and controlling the molar ratio of Al to Mn in the leaching solution to be 2: 1, completely reducing and leaching the anode material; adding 1.0mol/L hydrochloric acid aqueous solution, controlling the concentration of hydrochloric acid to be 0.5mol/L, and completing the reduction leaching process within 8 hours; filtering and separating insoluble residues in the leaching solution to ensure that the leaching rate of the valuable metals reaches 99 percent.
Adding 100mL of 2mol/L sodium chlorate solution into the leaching solution in batches, controlling the temperature of the leaching solution to be 90 ℃, and completely oxidizing manganese chloride in the leaching solution into manganese dioxide precipitate; filtering and separating the generated manganese dioxide precipitate, and washing with deionized water to remove salt carried by the manganese dioxide. Adding 5.0mol/L sodium hydroxide solution 1.0L to the leaching solution to neutralize the leaching solution to pH6-8 to produce LiCl2﹒2Al(OH)3Precipitating the double salt; the LiCl produced was separated by filtration2﹒2Al(OH)3Precipitating the double salt, and washing with deionized water to remove the salt.
Separating the filtered manganese dioxide precipitate and LiCl2﹒2Al(OH)3Mixing and grinding the double salt precipitate, drying at the temperature of 110-; soaking and delithiating with 0.5mol/L hydrochloric acid 1.0L, washing the salt content with deionized water, and drying at 110-130 deg.C to obtain 65g of Al, Co and Ni co-doped manganese series lithium ion sieve with chemical composition of H1.33Co0.01Ni0.01Al0.05Mn1.6O4﹒1.6Al2O3(ii) a The lithium adsorption capacity of the lithium ion battery is 18.5mg/g measured in 0.5g/L lithium chloride aqueous solution, and the manganese dissolution rate is 0.8-1% after 10 times of adsorption and desorption.
Example 2
Neutralizing to the pH value of 6-8 after the waste ternary lithium ion battery anode material is reduced and leached, filtering insoluble residues, wherein the leaching solution comprises the following valuable metals: ni15 g/L, Co18 g/L, Mn12 g/L and Li5.6 g/L, Al4 g/L. Enabling 200mL of impurity-removed leaching solution to pass through a filler column filled with 50g of manganese-doped lithium ion sieve, enabling lithium ions in the leaching solution to be selectively adsorbed by the manganese-doped lithium ion sieve, controlling the flow rate of the leaching solution to enable the lithium ion sieve to reach saturation adsorption for 4 hours, and then washing the manganese-doped lithium ion sieve with water to remove cobalt, nickel and manganese salt attached to the surface of the manganese-doped lithium ion sieve. And (3) slowly leaching the saturated and adsorbed manganese-doped lithium ion sieve by using 300mL of 0.5mol/L hydrochloric acid solution until the desorption rate of lithium ions reaches 99%, washing the manganese-doped lithium ion sieve by using deionized water, entering the next lithium adsorption cycle, and performing adsorption and desorption cycles for 10 times, wherein the manganese dissolution loss rate of the manganese-doped lithium ion sieve is 0.8% -1%.
Concentrating 3L of eluent doped with a manganese lithium ion sieve to 1.5L, adding a sodium carbonate solution to adjust the pH of the solution to 11, filtering precipitated cobalt, nickel and manganese impurities to obtain a refined lithium carbonate solution, adding an excessive sodium carbonate solution to adjust the pH of the solution to 14, converting lithium chloride in the solution into insoluble lithium carbonate to precipitate, filtering, washing and drying the lithium carbonate precipitate to obtain a battery-grade lithium carbonate product, recycling the mother solution, wherein the recovery rate of lithium salt in the leaching solution is 95%. Adding a sodium carbonate solution into the leaching solution from which the lithium salt is separated to enable cobalt-nickel-manganese salt in the leaching solution to generate carbonate precipitate, filtering and separating the precipitate, washing and drying to obtain cobalt-nickel-manganese carbonate which is used as a raw material for preparing the ternary lithium ion battery material again, and performing wastewater treatment after the mother solution is recycled.

Claims (2)

1. A preparation method of a lithium ion sieve is characterized in that an aluminum, cobalt and nickel co-doped manganese lithium ion sieve is prepared by taking a waste ternary lithium ion battery anode material as a raw material, the recovery rate of lithium and manganese components with high recovery difficulty reaches 85% and 98% of the industrial standard requirement, so that the economic benefit is improved, and the problem of heavy metal manganese pollution is solved.
(1) The reduction leaching of the anode material is to add commercial waste ternary lithium ion battery anode material powder with valuable metals of which the mass components are Ni 15-20%, Co 15-18%, Mn 10-18%, Li 4-8% and Al 4-10% into 0.5-1.0mol/L hydrochloric acid aqueous solution under stirring in batches, react aluminum in the anode material powder with hydrochloric acid to generate aluminum chloride, reduce high-valence-state nickel cobalt lithium manganate into cobalt chloride, nickel chloride, manganese chloride and lithium chloride under an acidic condition, replenish an aluminum powder reducing agent at the leaching solution temperature of 60-90 ℃, and control the Al/Mn molar ratio in the leaching solution to be 1.7-3: 1, completely reducing and leaching the anode material; replenishing hydrochloric acid aqueous solution, controlling the concentration of hydrochloric acid to be 0.5-1.0mol/L, and completing the reduction leaching process within 4-12 h; filtering and separating insoluble residues in the leaching solution to ensure that the leaching rate of valuable metals reaches 98-100 percent;
(2) separating manganese salt in the leaching solution by adding a sodium chlorate solution into the leaching solution in batches, controlling the temperature of the leaching solution to be 60-90 ℃, controlling the molar ratio of sodium chlorate to manganese to be 0.5-0.6:1, and completely oxidizing manganese chloride in the leaching solution into manganese dioxide precipitate; controlling the concentration of hydrochloric acid in the leaching solution to be 0.3-0.7mol/L so as to avoid the release of a large amount of chlorine and the reduction and dissolution of manganese dioxide by hydrochloric acid in the oxidation process; filtering the generated manganese dioxide precipitate, and washing with deionized water to remove salt carried by the manganese dioxide;
(3) the lithium salt is separated from the leaching solution by adding sodium hydroxide solution to the leaching solution to neutralize the leaching solution to pH6-8, only in this caseThe aluminum hydroxide can form precipitate, and the aluminum hydroxide can selectively adsorb lithium chloride in the leaching solution to generate LiCl2﹒2Al(OH)3Precipitating the double salt; cobalt salt and nickel salt are adsorbed in the aluminum hydroxide precipitation process; the LiCl produced was separated by filtration2﹒2Al(OH)3Precipitating the double salt, and washing with deionized water to remove the salt carried by the double salt;
(4) the manganese-based lithium ion sieve is prepared by filtering and separating the above manganese dioxide precipitate and LiCl2﹒2Al(OH)3Mixing and grinding the double salt precipitate, controlling the molar ratio of Li/Mn in the mixture to be 0.85-1.0, drying at the temperature of 110-; soaking and delithiating with 0.5mol/L hydrochloric acid, washing the salt content with deionized water, and drying at 110-130 ℃ to obtain the aluminum, cobalt and nickel co-doped manganese lithium ion sieve with the chemical composition of H1.33CoxNiyAlzMn1.67-x-y-zO4﹒nAl2O3Wherein x =0.01-0.05, y =0.01-0.05, z =0.01-0.05, n = 1.3-2.5; the lithium adsorption capacity of the lithium ion battery is 15-21mg/g measured in 0.5g/L lithium chloride aqueous solution, and the manganese dissolution rate is 0.8% -1% after 10 times of adsorption and desorption.
2. An application method of a lithium ion sieve is characterized in that an aluminum, cobalt and nickel co-doped manganese lithium ion sieve prepared by taking a waste ternary lithium ion battery positive electrode material as a raw material is applied, and a method for selectively adsorbing and extracting lithium from a waste ternary lithium ion battery positive electrode material leaching solution is adopted, wherein lithium salt is firstly selectively adsorbed and separated, so that entrainment loss during cobalt-nickel-manganese separation is avoided, and high recovery rate of lithium is ensured, so that other valuable metals such as cobalt, nickel and manganese can be efficiently separated according to a traditional precipitation method or an extraction method, and the recovery rate of 98% required by industrial specifications is achieved, so that economic benefits are improved, and the problem of heavy metal pollution is solved.
(1) The reduction leaching of the anode material is to leach the anode material after carbothermic reduction, catalytic reduction and chemical reduction with an aqueous solution, or to neutralize the anode material to the pH of 6-8 after leaching with an aqueous solution of sulfuric acid, hydrochloric acid or nitric acid, and to filter insoluble residues, wherein the composition of an impurity removal leaching solution is as follows: ni10-19 g/L, Co15-19 g/L, Mn8-19 g/L, Li2-9g/L, Al2-9 g/L;
(2) the lithium salt selective adsorption separation is to pass the impurity-removed leaching solution through a lithium ion sieve packing column to ensure that lithium ions in the leaching solution are selectively adsorbed by the manganese-doped lithium ion sieve, control the flow rate of the leaching solution to ensure that the lithium ion sieve reaches saturated adsorption for 4-12h, and then wash the manganese-doped lithium ion sieve by water to remove cobalt, nickel and manganese salt attached to the surface of the manganese-doped lithium ion sieve;
(3) the regeneration of the lithium ion sieve is to slowly drip and wash the saturated and adsorbed manganese-doped lithium ion sieve by 0.5mol/L hydrochloric acid solution, the desorption rate of the lithium ions reaches 90 to 98 percent, the manganese-doped lithium ion sieve is washed by water and enters the next lithium adsorption cycle for 10 times of adsorption and desorption cycles, and the manganese dissolution loss rate of the manganese-doped lithium ion sieve is 0.8 to 1 percent;
(4) the preparation of lithium carbonate is to concentrate eluent doped with manganese lithium ion sieve, add sodium carbonate solution to adjust the pH of the solution to 11, filter the precipitated cobalt, nickel and manganese impurities and obtain refined lithium carbonate solution; adding excessive sodium carbonate solution to adjust the pH value of the solution to 14 so as to convert lithium chloride in the solution into insoluble lithium carbonate precipitate; filtering, washing and drying the lithium carbonate precipitate to obtain a battery-grade lithium carbonate product, wherein the mother liquor can be recycled to ensure that the recovery rate of lithium in the leaching solution reaches 95-99%;
(5) the separation of cobalt-nickel-manganese compound is that one of sodium oxalate saturated solution, sodium carbonate solution or sodium hydroxide solution is added into leaching solution from which lithium salt is separated, so that cobalt-nickel-manganese salt in the leaching solution generates one of oxalate precipitate, carbonate precipitate or hydroxide precipitate, the precipitate is filtered and separated, washed and dried to obtain cobalt-nickel-manganese insoluble compound, which is used as raw material for preparing ternary lithium ion battery material again, and the mother solution is recycled for wastewater treatment.
CN202110903980.6A 2021-08-06 2021-08-06 Preparation and application method of lithium ion sieve Withdrawn CN113548701A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116002736A (en) * 2022-12-29 2023-04-25 四川顺应锂材料科技有限公司 Method for preparing aluminum hydroxide by pressure leaching and separating aluminum and lithium from clay lithium ore
CN117101596A (en) * 2023-08-11 2023-11-24 四川大学 Multi-metal doped hybrid manganese-based lithium ion sieve adsorbent and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116002736A (en) * 2022-12-29 2023-04-25 四川顺应锂材料科技有限公司 Method for preparing aluminum hydroxide by pressure leaching and separating aluminum and lithium from clay lithium ore
CN117101596A (en) * 2023-08-11 2023-11-24 四川大学 Multi-metal doped hybrid manganese-based lithium ion sieve adsorbent and preparation method thereof
CN117101596B (en) * 2023-08-11 2024-04-05 四川大学 Multi-metal doped hybrid manganese-based lithium ion sieve adsorbent and preparation method thereof

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