CN113430395A - Method for extracting lithium from waste lithium ion battery material by using lithium ion sieve - Google Patents

Method for extracting lithium from waste lithium ion battery material by using lithium ion sieve Download PDF

Info

Publication number
CN113430395A
CN113430395A CN202110735180.8A CN202110735180A CN113430395A CN 113430395 A CN113430395 A CN 113430395A CN 202110735180 A CN202110735180 A CN 202110735180A CN 113430395 A CN113430395 A CN 113430395A
Authority
CN
China
Prior art keywords
lithium
lithium ion
ion sieve
carbonate
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110735180.8A
Other languages
Chinese (zh)
Inventor
葛梦丹
韩璐
周蕾
袁永顺
王雪
刘炳光
李建生
石代龙
隋雨涵
张嘉铖
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin Vocational Institute
Original Assignee
Tianjin Vocational Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tianjin Vocational Institute filed Critical Tianjin Vocational Institute
Priority to CN202110735180.8A priority Critical patent/CN113430395A/en
Publication of CN113430395A publication Critical patent/CN113430395A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Secondary Cells (AREA)

Abstract

The invention relates to a method for extracting lithium from waste lithium ion battery materials by using a lithium ion sieve, which comprises the steps of uniformly mixing a cobalt nickel lithium manganate ternary lithium ion battery positive electrode material with urea or urea-formaldehyde resin, and carrying out pretreatment at the temperature of 100-300 ℃ so as to thermally reduce the ternary lithium ion battery positive electrode material into low-valence cobalt nickel manganese oxide, lithium oxide and lithium carbonate. With CO2The saturated aqueous solution leaches cobalt nickel manganese oxide, lithium oxide and lithium carbonate, lithium salt in the cobalt nickel manganese oxide, lithium oxide and lithium carbonate is dissolved into leaching solution in the form of lithium bicarbonate and lithium carbonate, a manganese lithium ion sieve prepared from waste lithium ion battery materials is used for absorbing and extracting lithium, then dilute hydrochloric acid is used for eluting lithium, and lithium chloride desorption solution is further carbonized by sodium carbonate to prepare a battery-grade lithium carbonate product. The invention has high lithium recovery rate, high adsorption selectivity and low production costLow cost and has industrial application prospect.

Description

Method for extracting lithium from waste lithium ion battery material by using lithium ion sieve
Technical Field
The invention relates to a method for extracting lithium from a waste lithium ion battery material by using a lithium ion sieve, in particular to a method for extracting lithium from a waste cobalt nickel lithium manganate ternary lithium ion battery positive material by using a lithium ion sieve, belonging to the fields of chemical industry and new energy.
Technical Field
Lithium extraction of the waste cobalt nickel lithium manganate ternary lithium ion battery is mainly focused on lithium extraction of a positive electrode material with high lithium content and great economic benefit, and the cost of pretreatment and leaching processes in the lithium extraction process can be shared because the economic value of cobalt salt and nickel salt extracted simultaneously is very high. The lithium extraction method of the anode material of the waste ternary lithium ion battery is divided into three types of a fire method, a wet method and a pretreatment and wet method.
The pyrogenic process lithium extraction is to utilize the sublimation property of lithium oxide at the high temperature of nearly 1000 ℃ to volatilize and separate the lithium oxide from the anode material of the waste ternary lithium ion battery at high temperature. The pyrogenic process is relatively simple, but the equipment investment and energy consumption are huge, and the lithium recovery rate is relatively low. Adding inorganic acid and inorganic salt auxiliary agent for roasting, which can properly reduce the decomposition temperature of the waste lithium battery material, but in the presence of SO2NOx or Cl2And (5) tail gas pollution treatment.
The wet lithium extraction is to separate lithium salt from the water solution of the anode material of the waste ternary lithium ion battery by using the traditional processes of leaching, precipitation, extraction, adsorption and the like. The wet process is complex, but the equipment is simpler, and China generally adopts the wet lithium extraction process. In the lithium salt leaching process, a large amount of chemical raw materials such as acid, alkali, complexing agent and the like are consumed, the amount of acid-alkali waste liquid is large, and secondary pollution exists. Since the lithium salt cannot be selectively recovered. The recovery rate of lithium salt is about 70%, and the lithium salt can not reach more than 85% of the requirement of the industry specification.
The cobalt nickel manganese lithium oxide in the anode material of the waste cobalt nickel lithium manganate ternary lithium ion battery exists in a high valence state, has low solubility in an aqueous solution, and cannot be quickly dissolved or leached out even a large amount of acid or alkali is added. In the prior art, a large amount of expensive hydrogen peroxide chemical reducing agent and a polybasic organic acid complexing agent are generally selected and added to dissolve a positive electrode material under a less harsh reaction condition, and then cobalt, nickel, manganese and lithium are respectively recovered by using the traditional methods of leaching, precipitation, extraction or adsorption and the like. Because the cost of extracting lithium from the anode material of the waste cobalt nickel lithium manganate ternary lithium ion battery is far higher than the cost of extracting lithium from original ore and brine, some recovery enterprises only pay attention to the recovery of cobalt salt and nickel salt with higher economic benefit, and lithium salt with high recovery cost is discharged along with waste water and buried along with waste residues, so that the waste of lithium resources is caused.
In recent years, the 'fire pretreatment and wet process' lithium extraction process is widely concerned, and has the advantages that the lithium recovery rate is up to more than 90%, the defects that a large amount of magnetic components are mixed in the finally produced lithium carbonate product, the product quality cannot directly reach the standard of battery-grade lithium carbonate, and the process technology economy needs to be further improved.
In addition, in the prior art, the reducing agent pretreated by a pyrogenic process mainly adopts a carbon material with weak reducibility, only at a higher pretreatment temperature, the stable structure of the anode material of the waste cobalt nickel lithium manganate ternary lithium ion battery can be completely destroyed by carbon reduction, and the volatilization loss and the residue entrainment loss of lithium salt are still large during high-temperature reduction pretreatment.
In order to overcome the defects of the existing precipitation and extraction lithium extraction technology, attention is paid to lithium extraction from waste lithium battery materials by adopting a lithium ion sieve adsorption method. In the early Chinese patent CN1200475C (2005-05-04) of Wuhan university of Engineers, a method for separating and recovering lithium from waste lithium ion batteries by using a lithium ion sieve is provided, and lambda-MnO is selected2The lithium ion sieve is used as an adsorbent to selectively adsorb lithium ions in the treated acid solution of the waste lithium ion battery, but the lithium ion sieve product and the application technical conditions are not disclosed.
The Chinese patent CN103045870B (2014-03-26) also proposes the use of lambda-MnO2Leaching solution of lithium ion sieve for waste lithium ion battery materialSelective adsorption is carried out to separate lithium from cobalt, nickel and manganese, and the lithium ion sieve product and the application technical conditions are not disclosed.
The research institute of process engineering of Chinese academy of sciences reports that the anode material of waste ternary lithium battery which is subjected to carbon reduction pretreatment is leached by adopting ammonia-ammonium bicarbonate medium in the presence of hydrogen peroxide to convert the anode material into soluble salt, then a manganese lithium ion sieve is used for absorbing and extracting lithium, the lithium ion sieve is used for removing lithium by using dilute hydrochloric acid, and the lithium-removed solution is further carbonized to obtain lithium carbonate. The performance and application technical conditions of the lithium ion sieve are not disclosed, and the recovery rate of lithium does not reach 85 percent of the specification requirement.
With the implementation of national waste lithium ion battery treatment industry specifications and the continuous rising of lithium salt price, industrial enterprises urgently need a new technology for extracting lithium from a waste ternary lithium ion battery anode material, wherein the new technology is technically economical and feasible.
Disclosure of Invention
In order to improve the recovery rate of lithium extracted from the anode material of the waste cobalt nickel lithium manganate ternary lithium ion battery, firstly, the pretreatment temperature of the material needs to be reduced to be lower than 600 ℃ so as to reduce the high-temperature volatilization loss of lithium oxide; secondly, lithium salt in the pretreated material can be completely leached out; the third requirement is that lithium separation is firstly carried out, so that the entrainment loss of lithium salt in the cobalt-nickel-manganese separation process is avoided, and the lithium recovery rate can reach more than 90% only in three pipelines.
Aiming at the problem that the lithium recovery rate is only about 70 percent and cannot meet the basic requirement of 85 percent in the prior art, the inventor provides a novel method for extracting lithium from the anode material of the waste cobalt nickel lithium manganate ternary lithium ion battery, and a urea reducing agent is added in the pretreatment process, so that the reduction pretreatment temperature is greatly reduced; with CO2Lithium carbonate generated in the pretreatment process is leached by the saturated aqueous solution, so that the solubility of lithium salt is greatly improved, and the circulating volume of the leaching solution is reduced; and selectively adsorbing lithium salt in the leaching solution by adopting a lithium ion sieve to prevent cobalt, nickel and other impurities from being carried, and directly obtaining a battery-grade lithium carbonate product.
The invention relates to a method for extracting lithium from a waste lithium ion battery material by using a lithium ion sieve, in particular to a method for extracting lithium from a waste cobalt nickel lithium manganate ternary lithium ion battery positive material by using a lithium ion sieve, which comprises the steps of pretreatment, lithium salt leaching, lithium ion sieve adsorption, acid elution of lithium and preparation of 5 parts of battery-grade lithium carbonate.
The pretreatment is that the cobalt nickel manganese lithium ternary lithium ion battery anode material and the urea compound are uniformly mixed according to the mass ratio of 1:0.2-2, the temperature is slowly raised and heated for 1-4h at the temperature of 100-300 ℃, the stable structure of the cobalt nickel manganese lithium ternary material is damaged, the cobalt nickel manganese lithium oxide with high valence state in the anode material is thermally reduced into cobalt nickel manganese oxide with low valence state, lithium oxide and lithium carbonate, and the urea compound is thermally decomposed into nitrogen and CO2The lithium salt formed by the thermal decomposition reaction is easily leached by the aqueous solution; the urea compound is one of urea, waste liquid containing urea, biuret, semicarbazide, urea-formaldehyde resin or waste liquid containing urea-formaldehyde resin.
Because the urea compound has stronger reducibility, the cobalt nickel lithium manganate can be completely reduced near the decomposition temperature, thereby avoiding the sublimation loss of lithium oxide during the carbon reduction roasting at the temperature of more than 600 ℃, and improving the recovery rate of lithium salt. Excessive urea compounds can be catalytically decomposed into nitrogen and CO by heavy metal at the high temperature of 220-300 DEG C2And the subsequent leaching process of the pretreated material is not influenced. Nitrogen and CO produced by slow thermal decomposition of urea compounds2The method can maintain the reaction materials in the reducing atmosphere, can maintain the cobalt nickel manganese oxide to be stably in the form of low-valence oxide or carbonate, and prevent the cobalt nickel manganese oxide from being excessively reduced into metal to cause difficulty in subsequent processing.
The decomposition temperature of the urea is 160 ℃, the decomposition temperature of the urea derivative is less than 300 ℃, and the cobalt, nickel and manganese with high valence can be reduced only by 100-300 ℃ so that the cobalt, nickel and manganese can be dissolved and leached into an aqueous solution.
According to the invention, after the pretreatment temperature is reduced to be within 300 ℃, the volatilization loss of lithium salt is greatly reduced, the energy consumption in the pretreatment process is also greatly reduced, the condition that cobalt and nickel are over-reduced into metal is not easy to occur, hydrogen peroxide is not needed for auxiliary leaching during subsequent separation of cobalt and nickel components, and the consumption of high-value chemical raw materials is reduced.
Extraction of lithium saltWith CO2And leaching the mixture of the cobalt nickel manganese oxide, the lithium oxide and the lithium carbonate in a low-valence state for 2-8h by using a saturated aqueous solution to dissolve lithium salt in the aqueous solution in the form of lithium bicarbonate and lithium carbonate, wherein the pH of a leaching solution is 9-13, and the solid-liquid mass ratio in the leaching solution is 1:4-20 to ensure that the lithium salt is completely dissolved.
CO periodically introduced in the invention2The gas converts the lithium carbonate in the leaching solution into the lithium bicarbonate with high solubility, the solubility of the lithium carbonate in the aqueous solution can be improved from 1.3g to 6.0g, the circulation volume of the leaching solution is greatly reduced, and the subsequent adsorption of a lithium ion sieve is facilitated.
The lithium ion sieve adsorption is to make the filtered and clarified leaching solution pass through a lithium ion sieve packing column to make Li in the leaching solution+Selectively adsorbing by a lithium ion sieve, controlling the flow rate of leaching solution to enable the lithium ion sieve to reach saturated adsorption for 4-12h, and then washing the lithium ion sieve by water to remove cobalt, nickel and manganese salt attached to the surface of the lithium ion sieve; the lithium ion sieve is a powdery or processed manganese series lithium ion sieve and is prepared by taking waste lithium ion battery material as a raw material at low cost, and the chemical composition of the lithium ion sieve is H1.33Alx Mn1.67O4﹒yAl2O3Wherein x =0.03-0.33, y =0.06-0.18, and the lithium ion saturated adsorption capacity is 48-54 mg/g; the adsorption and desorption circulation is carried out for 10 times, and the change of the adsorption capacity of the lithium ion sieve is less than 1 percent.
In the invention, the lithium ion sieve is adopted for absorbing and extracting lithium, and due to the high selectivity of the lithium ion sieve, the lithium ion extracting process is not influenced by trace cobalt salt, nickel salt and manganese salt existing in the leaching solution. After the leaching solution is recycled for multiple times, a small amount of cobalt salt, nickel salt and manganese salt accumulated in the leaching solution are precipitated and separated in the form of carbonate, and no lithium salt is carried in the precipitate, so that the problem of low lithium recovery rate in the existing lithium extraction process is solved.
The acid elution lithium is to slowly elute the saturated and adsorbed lithium ion sieve by using 0.5mol/L hydrochloric acid solution until the concentration of lithium salt in the subsequent effluent of the eluent is not changed, the desorption rate of lithium ions reaches 90-95 percent, the lithium ion sieve is washed by water and enters the next lithium adsorption cycle for 10 times of adsorption and desorption cycles, and the dissolution loss of the lithium ion sieve is less than 1 percent.
The preparation of lithium carbonate is that lithium ion sieve eluent is concentrated, sodium carbonate solution is added to adjust the pH value of the solution to 11, refined lithium carbonate solution is obtained by precipitating cobalt, nickel and manganese impurities in the lithium carbonate solution, and Li in the refined lithium carbonate solution is controlled+/Co2+、Li+/Ni2+And Li+/Mn2+Are all larger than 50; and adding an excessive sodium carbonate solution to adjust the pH value of the solution to 14, converting lithium chloride in the solution into insoluble lithium carbonate to be precipitated, filtering, washing and drying the lithium carbonate precipitate to obtain a battery-grade lithium carbonate product, wherein the recovery rate of lithium is 90-99%, and dilute hydrochloric acid is added into the mother solution to be used as an acid washing desorption solution for recycling.
In the invention, CO is introduced2The originality of improving the solubility of lithium carbonate in the aqueous solution originates from that the calcium carbonate solubility is increased by generating calcium bicarbonate after introducing carbon dioxide gas into the calcium carbonate aqueous solution in the basic chemistry. Experiments have shown that lithium carbonate also has calcium carbonate-like properties, which cobalt carbonate, nickel carbonate and manganese carbonate do not have. Introducing CO2Then the lithium carbonate is converted into lithium bicarbonate, the solubility of the lithium carbonate can be increased by nearly 6 times, and the lithium carbonate is heated to drive CO dissolved in the aqueous solution2Then, the lithium bicarbonate is converted into lithium carbonate to be precipitated and crystallized. Introducing CO2After that, the content of cobalt, nickel and manganese impurities in the solution is not correspondingly increased. By utilizing the property, the solubility of the lithium salt in the leaching solution can be improved, and the content of cobalt, nickel and manganese magnetic impurities in the lithium carbonate product is reduced, so that the lithium carbonate product meets the quality standard of battery-grade lithium carbonate.
The water leaching slag mainly comprises low-valence CoO, NiO, MnO and a small amount of CoCO3、NiCO3、MnCO3They can be easily dissolved in dilute sulfuric acid solution and separated and recovered by conventional extraction or precipitation methods.
The invention has the beneficial effects that:
(1) the urea compound with strong reducibility and low price is adopted to replace carbon as a reducing agent, so that the pretreatment temperature is reduced, the volatilization loss of lithium salt is reduced, the lithium recovery rate is improved, and energy is saved;
(2) CO periodically introduced2Gas lithium carbonate in leaching solutionThe salt is converted into alkalescent lithium bicarbonate, so that the solubility of the lithium bicarbonate in the aqueous solution is increased, and the circulation volume of the leaching solution is greatly reduced;
(3) the lithium ion sieve is used for extracting lithium from waste ternary lithium ion battery materials, has the advantages of high adsorption selectivity, high lithium recovery rate, recyclable mother liquor leaching and low production cost, can directly obtain a battery-grade lithium carbonate product, and has an industrial application prospect.
In order to reduce the content of a cobalt component and properly improve the lithium-containing compensation performance of a nickel component, the ternary lithium ion battery produces a high-nickel lithium ion battery; in order to reduce the production cost, some enterprises greatly improve the content of the manganese component. The waste ternary lithium ion battery anode material powder is obtained by stripping a ternary anode pole piece, and comprises the components of Li 6-8%, Ni 20-30%, Co 20-25%, Mn 15-30% and Al 2-3%.
The experimental raw material anode material of the waste ternary lithium ion battery is obtained from a network purchased industrial product or a self-disassembled ternary lithium ion battery. Urea, urea-formaldehyde resin, hydrochloric acid and CO2Are all commercial products.
Detailed Description
Example 1
100g of cobalt nickel lithium manganate ternary lithium ion battery positive electrode material (containing 6.9 g of lithium) and 20g of urea are uniformly mixed, put into a vacuum high-temperature furnace, heated to 300 ℃ within 1-2h, and subjected to heat preservation reaction at 300 ℃ for 0.5h, so that the positive electrode material is thermally reduced into low-valence cobalt nickel manganese oxide, lithium oxide and lithium carbonate, and the urea is completely decomposed and volatilized. The pretreated positive electrode material was immersed in 2000g of water for 2-4 hours, and the lithium oxide and lithium carbonate therein were leached into an aqueous solution with stirring. Introducing CO into the leaching solution2And (4) until the lithium carbonate is saturated, converting the lithium carbonate into lithium bicarbonate and promoting the leaching of the lithium carbonate. Filtering and separating the cobalt-nickel-manganese oxide leaching residue, and washing the leaching residue with water to obtain 1.95L leaching solution containing 3.5g/L lithium, wherein the recovery rate of lithium leaching is 99 percent.
Passing the clarified leachate through a column packed with 150g of manganese-based lithium ion sieve to remove Li from the leachate+Is selectively adsorbed by the lithium ion sieveAnd after 4h, saturated adsorption is achieved, the lithium ion sieve is cleaned by water, cobalt, nickel and manganese salt attached to the surface of the lithium ion sieve is removed, 2.1L of low-concentration lithium-containing solution containing 0.04g/L of lithium is obtained, the low-concentration lithium-containing solution is circularly used for leaching the anode material, and the adsorption capacity of the lithium ion sieve is calculated to be 45 mg/g.
And (3) leaching the saturated and adsorbed lithium ion sieve by using 2L of 0.5mol/L hydrochloric acid solution, and washing the lithium ion sieve by using water to obtain 2L of lithium ion sieve desorption solution containing 3.2g/L lithium, wherein the lithium ion desorption rate reaches 95%, the desorbed lithium ion sieve is used for the next lithium adsorption and desorption cycle, and the dissolution loss of the lithium ion sieve is less than 1%.
Concentrating the lithium ion sieve eluent to 0.5L, adding a sodium carbonate solution with the mass concentration of 10% to adjust the pH of the solution to 11, and filtering and removing cobalt, nickel and manganese impurities in a carbonate precipitation form to obtain a refined lithium chloride solution. Adding a sodium carbonate solution with the mass concentration of 10% into the lithium chloride solution to adjust the pH value of the solution to be 14 to obtain a lithium carbonate precipitate, filtering, washing and drying the lithium carbonate precipitate to obtain 28 g of a battery-grade lithium carbonate product, further concentrating the mother solution, and then recovering to obtain 4.9g of the battery-grade lithium carbonate product, wherein the recovery rate of lithium is 96%.
Example 2
100g of cobalt nickel lithium manganate ternary lithium ion battery positive electrode material (containing 6.9 g of lithium) and 30g of water-soluble urea-formaldehyde resin powder are uniformly mixed, put into a vacuum high-temperature furnace, heated to 300 ℃ within 1h, and subjected to heat preservation reaction at 300 ℃ for 1h, so that the positive electrode material is thermally reduced into low-valence cobalt nickel manganese oxide, lithium oxide and lithium carbonate, and the urea-formaldehyde resin is completely decomposed and volatilized. The pretreated positive electrode material was immersed in 2000g of water for 2-4 hours, and the lithium oxide and lithium carbonate therein were leached into an aqueous solution with stirring. Introducing CO into the leaching solution2And (4) until the lithium carbonate is saturated, converting the lithium carbonate into lithium bicarbonate and promoting the leaching of the lithium carbonate. Filtering and separating the cobalt-nickel-manganese oxide leaching residue, and washing the leaching residue with water to obtain 2.1L leaching solution containing 3.3g/L lithium, wherein the recovery rate of lithium leaching is 100 percent.
The clarified leachate was passed through a column packed with 150g of a manganese-based lithium ion sieve as described in example 1 to collect Li in the leachate+Is selectively adsorbed by the lithium ion sieve for 6 hoursSaturated adsorption, washing the lithium ion sieve with water, removing cobalt nickel manganese salt attached to the surface of the lithium ion sieve, obtaining 2.0L of low-concentration lithium-containing solution containing 0.05g/L lithium, which can be recycled for leaching the anode material, and calculating that the adsorption capacity of the lithium ion sieve is 45.3mg/g and the change of the adsorption capacity of the lithium ion sieve is less than 1%.
And (3) leaching the saturated and adsorbed lithium ion sieve by using 2L of 0.5mol/L hydrochloric acid solution, and washing the lithium ion sieve by using water to obtain 2.1L of lithium-containing 3.1g/L lithium ion sieve desorption solution, wherein the lithium ion desorption rate reaches 96%, the desorbed lithium ion sieve is used for the next lithium adsorption and desorption cycle, and the dissolution loss of the lithium ion sieve is less than 1%.
Concentrating the lithium ion sieve eluent to 0.5L, adding a sodium carbonate solution with the mass concentration of 10% to adjust the pH of the solution to 11, and filtering and removing cobalt, nickel and manganese impurities in a carbonate precipitation form to obtain a refined lithium chloride solution. Adding a sodium carbonate solution with the mass concentration of 10% into the lithium chloride solution to adjust the pH of the solution to be 14, and obtaining lithium carbonate precipitate. And filtering, washing and drying the lithium carbonate precipitate to obtain 29g of battery-grade lithium carbonate product, and recovering 4.5g of battery-grade lithium carbonate product after further concentrating the mother liquor, wherein the recovery rate of lithium is 96%.

Claims (6)

1. A method for extracting lithium from waste lithium ion battery materials by using a lithium ion sieve, in particular to a method for extracting lithium by using a lithium ion sieve in a waste cobalt nickel lithium manganate ternary lithium ion battery positive material, which is characterized by comprising 5 parts of pretreatment, lithium salt leaching, lithium ion sieve adsorption, acid elution lithium and battery-grade lithium carbonate preparation; the pretreatment is that the cobalt nickel lithium manganate ternary lithium ion battery anode material and urea compound are uniformly mixed according to the mass ratio of 1:0.2-2, the temperature is slowly raised and heated for 1-4h at the temperature of 100-300 ℃, the anode material is thermally reduced into cobalt nickel manganese oxide with low valence state, lithium oxide and lithium carbonate, and the urea compound is thermally decomposed into nitrogen and CO2(ii) a The urea compound is one of urea, waste liquid containing urea, biuret, semicarbazide, urea-formaldehyde resin or waste liquid containing urea-formaldehyde resin.
2. The method of claim 1, wherein the lithium ion sieve is usedThe method for extracting lithium from waste lithium ion battery materials is characterized in that CO is adopted for leaching lithium salt2And leaching the mixture of the cobalt nickel manganese oxide, the lithium oxide and the lithium carbonate in a low-valence state for 2-8h by using a saturated aqueous solution, so that the lithium salt is dissolved in the aqueous solution in the form of lithium bicarbonate and lithium carbonate, the pH of a leaching solution is 9-13, and the solid-liquid mass ratio in the leaching solution is 1: 4-20.
3. The method for extracting lithium from waste lithium ion battery materials by using the lithium ion sieve as claimed in claim 1, wherein the adsorption of the lithium ion sieve is to pass the filtered and clarified leaching solution through a lithium ion sieve packing column to enable Li in the leaching solution to be in the form of Li+Selectively adsorbing by a lithium ion sieve, controlling the flow rate of leaching solution to enable the lithium ion sieve to reach saturated adsorption for 4-12h, and then washing the lithium ion sieve by water to remove cobalt, nickel and manganese salt attached to the surface of the lithium ion sieve.
4. The method for extracting lithium from waste lithium ion battery materials according to claims 1 and 3, characterized in that the lithium ion sieve is a powdery or formed manganese-based lithium ion sieve, and is prepared from waste lithium ion battery materials as raw materials at low cost, and the chemical composition of the lithium ion sieve is H1.33Alx Mn1.67O4﹒yAl2O3Wherein x =0.03-0.33, y =0.06-0.18, and the lithium ion saturated adsorption capacity is 45-54 mg/g; the adsorption and desorption circulation is carried out for 10 times, and the change of the adsorption capacity of the lithium ion sieve is less than 1 percent.
5. The method for extracting lithium from waste lithium ion battery materials by using the lithium ion sieve in claim 1, wherein the step of acid elution of lithium is to slowly elute the saturated and adsorbed lithium ion sieve by using 0.5mol/L hydrochloric acid solution, the desorption rate of lithium ions reaches 90% -98%, the lithium ion sieve is washed by water, the next lithium adsorption cycle is carried out, the adsorption and desorption cycle is carried out for 10 times, and the dissolution loss of the lithium ion sieve is less than 1%.
6. The method of claim 1, wherein the lithium ion sieve is used to extract lithium from the waste lithium ion battery material, and the lithium carbonate is prepared by separating lithium ionsConcentrating the eluate, adding sodium carbonate solution to adjust pH to 11 to precipitate cobalt nickel manganese impurity to obtain refined lithium carbonate solution, and controlling Li in the refined lithium carbonate solution+/Co2+、Li+/Ni2+And Li+/Mn2+Are all larger than 50; and adding an excessive sodium carbonate solution to adjust the pH value of the solution to 14, converting 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 recovery rate of lithium is 90-99%.
CN202110735180.8A 2021-06-30 2021-06-30 Method for extracting lithium from waste lithium ion battery material by using lithium ion sieve Pending CN113430395A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110735180.8A CN113430395A (en) 2021-06-30 2021-06-30 Method for extracting lithium from waste lithium ion battery material by using lithium ion sieve

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110735180.8A CN113430395A (en) 2021-06-30 2021-06-30 Method for extracting lithium from waste lithium ion battery material by using lithium ion sieve

Publications (1)

Publication Number Publication Date
CN113430395A true CN113430395A (en) 2021-09-24

Family

ID=77758107

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110735180.8A Pending CN113430395A (en) 2021-06-30 2021-06-30 Method for extracting lithium from waste lithium ion battery material by using lithium ion sieve

Country Status (1)

Country Link
CN (1) CN113430395A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114256526A (en) * 2021-11-22 2022-03-29 上海交通大学 Method for recovering battery-grade lithium carbonate from lithium ion battery positive electrode material
CN114480846A (en) * 2021-12-15 2022-05-13 河海大学 Method for recovering valuable metals in anode materials of waste lithium batteries
CN115999604A (en) * 2022-12-15 2023-04-25 广东省科学院生态环境与土壤研究所 Method for preparing efficient core-shell structure catalyst by taking tail end waste residue recovered from waste ternary lithium battery as raw material, product and application

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1451771A (en) * 2003-05-09 2003-10-29 武汉理工大学 Method for recovery of lithium from used lithium ion cell with ion sieve
CN111115712A (en) * 2019-12-24 2020-05-08 赵世福 Method for decomposing lithium cobaltate
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
CA3144711A1 (en) * 2019-07-26 2021-02-04 Wolfgang Rohde Process for the recovery of lithium from waste lithium ion batteries

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1451771A (en) * 2003-05-09 2003-10-29 武汉理工大学 Method for recovery of lithium from used lithium ion cell with ion sieve
CA3144711A1 (en) * 2019-07-26 2021-02-04 Wolfgang Rohde Process for the recovery of lithium from waste lithium ion batteries
CN111115712A (en) * 2019-12-24 2020-05-08 赵世福 Method for decomposing lithium cobaltate
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

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114256526A (en) * 2021-11-22 2022-03-29 上海交通大学 Method for recovering battery-grade lithium carbonate from lithium ion battery positive electrode material
CN114480846A (en) * 2021-12-15 2022-05-13 河海大学 Method for recovering valuable metals in anode materials of waste lithium batteries
CN115999604A (en) * 2022-12-15 2023-04-25 广东省科学院生态环境与土壤研究所 Method for preparing efficient core-shell structure catalyst by taking tail end waste residue recovered from waste ternary lithium battery as raw material, product and application

Similar Documents

Publication Publication Date Title
CN111519031B (en) Method for recycling nickel, cobalt, manganese and lithium from waste power lithium ion battery black powder
CN109809382B (en) Method for synthesizing iron phosphate by using waste phosphate generated by precipitating trace heavy metals
CN113430395A (en) Method for extracting lithium from waste lithium ion battery material by using lithium ion sieve
CN111118294A (en) Method for recycling valuable metals from waste lithium ion battery materials step by step
CN108963371B (en) Method for recovering valuable metals from waste lithium ion batteries
CN100469697C (en) Method for producing low-magnesium battery-stage lithium carbonate from lithium sulfate solution
CN112095003B (en) Method for recycling various valuable metals and acid-base double-medium regeneration cycle from laterite-nickel ore
CN113444885B (en) Method for preferentially extracting metal lithium from waste ternary lithium ion battery and simultaneously obtaining battery-grade metal salt
CN101899582A (en) Method for extracting vanadium pentoxide from vanadium slag
CN112522512B (en) Method for preparing battery-grade cobalt sulfate by using organic cobalt slag of zinc smelting plant
CN112280976B (en) Method for recycling valuable metals from laterite-nickel ore and regenerating and recycling acid
CN106340692A (en) A kind of method that cleaning reclaims lithium in positive electrode
CN112079369A (en) Method for preferentially extracting lithium and cooperatively recovering manganese from waste lithium ion battery
CN112520790A (en) Method for producing cobalt sulfate by using organic cobalt slag of zinc smelting plant
CN113793994B (en) Method for recycling waste lithium iron phosphate batteries
WO2023045331A1 (en) Method for selectively recovering valuable metal in waste lithium battery
WO2024000818A1 (en) Recovery method for spent lithium battery materials
CN110735032B (en) Vanadium-titanium-iron paragenetic ore treatment process
CN114436300A (en) Method for acidifying and leaching lithium by spodumene
CN117926027A (en) Comprehensive utilization method of laterite nickel ore
CN101693554A (en) Method for extracting vanadium pentoxide from stone coal ores
CN108910957A (en) A method of soft magnetism mangano-manganic oxide is produced using hydroquinone reduction electrolytic manganese anode mud
CN108910956A (en) A method of soft magnetism mangano-manganic oxide is produced using aniline reduction electrolytic manganese anode mud
CN113186400A (en) Method for recovering valuable metal from lithium ion battery
CN101358301A (en) Method for directly extracting vanadium from vanadium titan magnetite concentrate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20210924