CN118957276A - A method for extracting lithium from waste electrolyte and recycling it - Google Patents
A method for extracting lithium from waste electrolyte and recycling it Download PDFInfo
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- CN118957276A CN118957276A CN202411450322.6A CN202411450322A CN118957276A CN 118957276 A CN118957276 A CN 118957276A CN 202411450322 A CN202411450322 A CN 202411450322A CN 118957276 A CN118957276 A CN 118957276A
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
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- 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
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Abstract
本发明属于锂离子电池回收领域，具体涉及一种废弃电解质中提锂及回收利用的方法，主要包括如下步骤：S1：将锂电池进行放电、拆解获得正极废料；加入氢氧化钠浸泡，过滤后得到正极粉末；S2：将正极粉末采用浓度为0.3‑0.5mol/L的硫酸、30%的过氧化氢浸出，过滤后得到浸出液和浸出渣；S3：将浸出液以2BV/h的流速流经采用接枝有冠醚的吸附树脂为吸附介质的树脂柱；S4：采用稀盐酸对树脂进行解吸附，得到含锂溶液。本发明通过利用冠醚、氨基与树脂基体中特定孔结构三者之间的配合提高了树脂对锂离子的吸附能力及吸附选择性，将其应用于锂离子电池正极材料回收锂元素中，能够获得较高纯度的锂，且锂的回收率较高。
The present invention belongs to the field of lithium ion battery recovery, and is specifically related to a method for extracting lithium and recycling in a waste electrolyte, mainly comprising the following steps: S1: discharging and disassembling a lithium battery to obtain anode waste; adding sodium hydroxide to soak, and filtering to obtain cathode powder; S2: leaching the cathode powder with sulfuric acid and 30% hydrogen peroxide at a concentration of 0.3-0.5mol/L, and filtering to obtain a leachate and a leach residue; S3: the leachate is passed through a resin column using an adsorption resin grafted with a crown ether as an adsorption medium at a flow rate of 2BV/h; S4: desorbing the resin with dilute hydrochloric acid to obtain a lithium-containing solution. The present invention improves the adsorption capacity and adsorption selectivity of the resin to lithium ions by utilizing the coordination between the crown ether, amino and specific pore structures in the resin matrix, and is applied to the recovery of lithium elements from lithium ion battery cathode materials, and can obtain lithium of higher purity, and the recovery rate of lithium is higher.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery recovery, and particularly relates to a method for extracting lithium from waste electrolyte and recycling the lithium.
Background
The rapid development of new energy technology is leading to the transformation of global energy structure, wherein lithium ion batteries are used as a key technology, have been successfully commercialized, and are widely applied in various fields. Particularly in the new energy fields of electric automobiles, energy storage systems and the like, a lithium ion battery becomes an indispensable energy storage solution because of the advantages of high energy density, long cycle life, quick charging capability and the like. However, with the continuous expansion of the installed capacity of lithium ion batteries, the production of waste lithium ion batteries is also increasing year by year, which brings new environmental challenges.
After the waste lithium ion battery is abandoned, if the waste lithium ion battery is improperly treated, heavy metals such as lithium, cobalt, nickel and the like contained in the waste lithium ion battery, solvents and other organic auxiliary materials can cause serious pollution to the environments such as soil, water sources and the like. Meanwhile, the recovery and reuse of the waste lithium ion batteries have important economic and environmental values. Because the metal resources contained in the batteries are limited in reserves in the nature and the market price is high, the metal can be recovered, so that the exploitation requirements on new mineral resources can be reduced, the exploitation cost can be reduced, and the damage to the environment can be reduced. In addition, secondary pollution control and material recycling in the recovery process are also important components for realizing sustainable development and recycling economy.
The recovery treatment technology of the waste lithium ion battery mainly comprises three methods of physical separation, biochemical treatment and chemical treatment. Physical separation includes flotation and grinding. The biochemical treatment utilizes microorganisms to catabolize battery materials and selectively leach specific elements, but is still immature at present and is not practically applied. The chemical treatment method is a recovery treatment method widely used at present, and related researches are carried out more, and the chemical treatment method is mainly divided into three main types of a fire process, a wet process and electrode regeneration.
The method for recovering and extracting lithium of the lithium ion battery at the present stage mainly comprises a precipitation method, a membrane separation method, an adsorption method and the like. Coprecipitation of other metal ions is often generated during precipitation, separation difficulty is increased, cost is increased, and membrane separation method also has problems of membrane pollution and long separation time. The adsorption method for extracting lithium has the advantages of low cost, small environmental pollution, high extraction rate and easy continuous operation, but the selectivity, adsorption capacity and mass transfer rate of the common adsorbent still need to be further improved. Therefore, according to the structural characteristics of Li +, from the interaction of Li + with the adsorption site of the adsorbent, it is extremely important to study a novel adsorbent and to obtain high-purity Li +.
Crown ethers containing 12-14 membered rings are good Li + selective ligands. Currently, related researches adopt crown ether with 12-14 membered rings as a selective ligand of Li +, and the high internal phase surface is adopted to fix the Li + ligand through copolymerization or surface modification, for example, chinese patent document CN110227424A discloses a preparation method and application of a covalent modified high-density crown ether functionalized porous adsorbent; the method comprises the following steps: firstly, preparing a porous polymer PVBC and a porous polymer of surface branch polyglycidyl methacrylate, which is marked as PVBC-g-PGMA; PVBC-g-PGMA was mixed with DMF and 2AB12C4 was added after PVBC-g-PGMA was dispersed in DMF; washing the obtained product with DMF, ethanol and double distilled water in turn after water bath reaction, and drying in vacuum to obtain the amino ethyl benzo-12-crown-4 modified porous adsorbent; the porous adsorbent prepared by the invention effectively improves adsorption capacity and mass transfer efficiency, solves the problems of low density of active sites and deeper embedding of active sites of the existing lithium extraction adsorbent, and provides a new thought for developing an efficient lithium extraction adsorbent.
However, although the material has better Li + selectivity and adsorption kinetics performance, the process is complex on one hand, and the industrial application is difficult; on the other hand, the adsorption selectivity and the adsorption capacity of the lithium ion are still to be further improved.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides a method for extracting lithium from waste electrolyte and recycling the lithium, and the method can obtain higher recovery rate and purity of lithium element by adopting the adsorption resin grafted with crown ether as a specific lithium adsorbent, and further recycle the lithium element by subsequent process treatment.
An object of the present invention is to provide a method for extracting lithium from waste electrolyte, comprising the steps of:
S1: discharging and disassembling the lithium battery to obtain positive electrode waste; adding sodium hydroxide for soaking, wherein the liquid-solid ratio of the sodium hydroxide to the positive electrode waste is 3-10:1, and filtering to obtain positive electrode powder;
s2: leaching the positive electrode powder by adopting sulfuric acid with the concentration of 0.3-0.5mol/L and 30% hydrogen peroxide, and filtering to obtain leaching liquid and leaching slag;
Preferably, in order to assist in improving the recovery rate and purity of lithium ions, the method further comprises the step of adjusting the pH value of the system to 8.5 after the acid leaching process is finished, and filtering after precipitation, wherein the purpose is to remove impurity ions and improve the lithium content of the leaching solution.
S3: allowing the leaching solution to flow through a resin column adopting the adsorption resin grafted with crown ether as an adsorption medium at the flow rate of 2BV/h, detecting the lithium content in the effluent, and stopping leaching when the lithium content in the effluent is greater than 0.1 ug/L;
At this time, the resin column is in an adsorption saturated state.
The adsorption resin grafted with crown ether is prepared by the following method:
Preparing a resin precursor by taking Glycidyl Methacrylate (GMA), triallyl isocyanurate (TAIC), azodiisobutyronitrile and n-heptane as oil phases, taking water and polyvinyl alcohol as water phases and adopting a conventional suspension polymerization mode according to the mass ratio of the water phases to the oil phases being 3:1; adding the resin precursor into a mixed solution of 2-hydroxymethyl-12-crown-4 and sodium hydride, refluxing under nitrogen atmosphere, and drying to obtain crown-etherified adsorption resin; opening the epoxy ring of the crown ether adsorption resin by using ethylenediamine, filtering, cleaning and drying to obtain the adsorption resin grafted with crown ether;
S4: and desorbing the resin by adopting dilute hydrochloric acid to obtain a lithium-containing solution.
Further, in the step S1, the liquid-solid ratio of the sodium hydroxide to the positive electrode waste is 10:1.
Further, the specific conditions in step S2 are: adding the positive electrode powder obtained in the step S1 into a dilute sulfuric acid solution with the concentration of 0.3-0.5mol/L according to the liquid-solid ratio of 20mL-30mL:1g, leaching and extracting lithium, wherein 1mL of 30% hydrogen peroxide is added into the dilute sulfuric acid solution; leaching at 55-65deg.C for 120-200min, adjusting pH to 8.5, and filtering to obtain leaching solution and leaching residue.
Further, in the step S3, the rotation speed of suspension polymerization is 260r/min, the mass ratio of GMA to TAIC in the oil phase is 5:1, and the mass ratio of n-heptane to GMA is 1:3.
Further, in step S3, the temperature rising rate of the suspension polymerization is that the temperature rises to 85 ℃ at a rate of 2 ℃/min after stirring until the particle size is uniform, and the temperature is kept for 4 hours.
Further, the crown etherified adsorbent resin in step S3 is prepared by the following method:
Mixing 2-hydroxymethyl-12-crown-4 and sodium hydride according to a molar ratio of 1:1 to obtain a mixed solution, stirring at 55 ℃ for 6 hours under a nitrogen atmosphere, adding a resin precursor into the mixed solution, refluxing the resin precursor and the 2-hydroxymethyl-12-crown-4 for 70 hours under the protection of nitrogen, filtering, washing and drying to obtain the crown-etherified adsorption resin.
Further, the specific process conditions for ring opening of epoxy by adopting ethylenediamine in the step S3 are as follows:
Soaking the crown-etherified adsorption resin in DMF (dimethyl formamide), fully swelling for 24 hours, and obtaining crown-etherified resin according to the mass ratio: ethylenediamine is added in a ratio of 1:5, and the reaction is carried out for 5 hours at 70 ℃. And cooling, filtering, washing and airing after the reaction is finished to obtain the adsorption resin grafted with crown ether.
Further, the specific process of step S4 is as follows: and (3) disassembling the resin column adsorbed in the step (S3), immersing in 1mol/L dilute hydrochloric acid, stirring for 4-6h at 25 ℃ in a solid-to-liquid ratio of the resin to the dilute hydrochloric acid solution of 1:36-40, and obtaining the lithium-containing solution.
The invention also aims to provide a method for recycling the waste electrolyte after extracting lithium, which is characterized by comprising the following steps of: and adding the lithium-containing solution into sodium carbonate to obtain the battery-grade lithium carbonate.
It should be noted that, the lithium carbonate product is difficult to form under acidic condition in the known art, the alkaline agent commonly used in the art is added to adjust the pH value of the system to 7-11 during the preparation of lithium carbonate, and then carbonate is added to perform the preparation process of lithium carbonate, the function of the lithium-containing solution is two, namely, the excess acid in the lithium-containing solution can be neutralized, and the generation of lithium carbonate is facilitated under the alkaline condition, the alkaline agent in the invention is a common alkaline agent in the field, such as sodium hydroxide.
The invention has the following beneficial effects:
1. According to the invention, by means of the structural difference between Li + and impurity ions, glycidyl methacrylate is used as a monomer, triallyl isocyanurate is used as a polymerization crosslinking agent, n-heptane is used as a pore-forming agent, and the optimized component proportion is adopted, so that the precursor resin with proper pore size distribution can be obtained, and the abundant pore structure in the precursor resin can assist in improving the adsorption capacity and the adsorption selectivity to lithium to a certain extent in the leaching process.
2. According to the invention, the 2-hydroxymethyl-12-crown-4 is grafted on the precursor resin, so that crown ether groups are reserved in the resin precursor, the crown ether has electron-rich cavities, the cavity size is relatively close to the diameter of Li +, a very stable complex can be formed with lithium ions, the complex has relatively high ion interference resistance, and the complex has specific selective adsorptivity to lithium ions.
3. According to the invention, after 2-hydroxymethyl-12-crown-4 is grafted on the precursor resin, epoxy groups wrapped in the resin matrix are fully exposed through full swelling, then ethylenediamine is used as a functionalizing agent to open the ring of the epoxy, a certain amount of amino groups can be introduced on the resin matrix, and hydrogen ions generated when the crown ether groups on the resin matrix specifically adsorb lithium can be combined with the amino groups in the resin matrix, so that the adsorption capacity of the resin on lithium ions is further improved; the invention further improves the adsorption capacity and adsorption selectivity of the resin to lithium ions by utilizing the cooperation among crown ether, amino and a specific pore structure in the resin matrix, and the lithium ion resin can obtain high-purity lithium by applying the resin to the lithium element recovery of the positive electrode material of the lithium ion battery, and the recovery rate of the lithium is higher.
Drawings
FIG. 1 is an SEM spectrum of a crown ether grafted adsorbent resin prepared according to the present invention;
FIG. 2 is a graph showing pore size distribution of a crown ether grafted adsorbent resin prepared according to the present invention.
Detailed Description
The present application will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical scheme of the present application, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present application is not limited to the following examples. All other embodiments, based on the examples given, which a person of ordinary skill in the art would obtain without inventive faculty are within the scope of the application
It should be noted that the number of the substrates, the following crown ether grafted adsorption resins described in examples 1-3 were prepared as follows:
1000g of water phase (10 g of 5% polyvinyl alcohol and the balance of deionized water) is added into a three-port bottle, the mixture is stirred uniformly, the temperature is raised to 40 ℃, the oil phase (the polymerized monomer GMA: TAIC in the oil phase is 5:1, the initiator is azodiisobutyronitrile, the pore-forming agent is n-heptane, the mass ratio of n-heptane to GMA is 1:3) is added according to the mass ratio of 3:1 of the water phase to the oil phase, the mixture is stirred at the speed of 260 revolutions per minute, the temperature is raised to 85 ℃ at the speed of 2 ℃/min after the particle size is uniform, the temperature is kept for 4 hours, the mixture is filtered, the solvent is removed by Soxhlet extraction with petroleum ether as the solvent, and the mixture is dried, so that the resin precursor is obtained.
Mixing 2-hydroxymethyl-12-crown-4 and sodium hydride according to a molar ratio of 1:1, stirring for 6 hours at 55 ℃, stirring under nitrogen atmosphere, adding a resin precursor into the solution, refluxing for 70 hours under nitrogen protection, filtering, washing and drying to obtain the crown-etherified adsorption resin, wherein the mass ratio of the resin precursor to the 2-hydroxymethyl-12-crown-4 is 6:1.
And (3) soaking the crown-etherified adsorption resin in DMF (dimethyl formamide), fully swelling for 24 hours, and adding ethylenediamine according to the mass ratio of 1:5 to react for 5 hours at 70 ℃. And cooling, filtering, washing and airing after the reaction is finished, so as to obtain the adsorption resin grafted with crown ether.
The morphology of the prepared adsorption resin grafted with crown ether is characterized by adopting a scanning electron microscope, and the result is shown in figure 1.
The specific surface and pore canal analysis are determined by adopting a low-temperature (77K) nitrogen adsorption and desorption method. The sample is subjected to pretreatment under high-purity nitrogen gas before measurement, and the treatment condition is that the sample is purged for 13 hours at 120 ℃. The BELSORP-mini II adsorption instrument automatically obtains the average pore diameter of the resin which is 6.9nm and the specific surface area 1025m 2/g through the calculation of a formula by measuring the adsorption and degassing isotherm of nitrogen under the condition of 77K.
The amino content of the resin is measured by a hydrochloric acid titration method, and the amino content of the adsorption resin grafted with crown ether is 1.6mmol/g.
The content of crown ether in the resin is determined by adopting a gas chromatography-mass spectrometry (GC-MS), and the content of crown ether in the adsorption resin grafted with crown ether is 3.1mmol/g.
The lithium ion battery mainly comprises a negative plate, a diaphragm and a positive plate, wherein the positive plate takes aluminum foil as a current collector, and both sides of the positive plate are coated with positive electrode materials (active material+conductive agent+binder PVDF), and the positive electrode materials of the waste lithium ion battery adopted in the following embodiments have the content of Li of 7.4%, the content of Ni of 20.1%, the content of Co of 19.8% and the content of Mn of 21.3%.
Example 1
S1: discharging and disassembling the lithium battery to obtain positive electrode waste; and adding sodium hydroxide for soaking, and carrying out suction filtration to obtain the anode powder, wherein the liquid-solid ratio of the sodium hydroxide to the anode waste is 3:1.
S2: adding the positive electrode powder obtained in the step S1 into a dilute sulfuric acid solution with the concentration of 0.3mol/L according to the liquid-solid ratio of 20mL to 1g for leaching and extracting lithium, wherein 1mL of 30% hydrogen peroxide is added into the dilute sulfuric acid solution; leaching at 60 ℃ for 180min, adjusting the pH value of the system to 8.5, and filtering to obtain leaching liquid and leaching slag.
S3: and (3) allowing the leaching solution to flow through an adsorption column with the crown ether grafted adsorption resin as an adsorption medium at a flow rate of 2BV/h, detecting the lithium content in the effluent, and stopping leaching when the lithium content in the effluent is greater than 0.1ug/L, wherein the resin is in an adsorption saturated state.
S4: and (3) dismantling the resin column subjected to adsorption saturation in the step (S3), soaking in 1mol/L dilute hydrochloric acid, stirring for 4 hours at 25 ℃ in a solid-to-liquid ratio of the resin to the dilute hydrochloric acid of 1:36, and obtaining the lithium-containing solution.
Example 2
S1: discharging and disassembling the lithium battery to obtain positive electrode waste; and adding sodium hydroxide for soaking, and carrying out suction filtration to obtain the anode powder, wherein the liquid-solid ratio of the sodium hydroxide to the anode waste is 5:1.
S2: adding the positive electrode powder obtained in the step S1 into a dilute sulfuric acid solution with the concentration of 0.5mol/L according to the liquid-solid ratio of 25mL to 1g for leaching and extracting lithium, wherein 1mL of 30% hydrogen peroxide is added into the dilute sulfuric acid solution; leaching for 200min at 55 ℃, adjusting the pH value of the system to 8.5, and filtering to obtain leaching liquid and leaching slag.
S3: and (3) allowing the leaching solution to flow through an adsorption column with the crown ether grafted adsorption resin as an adsorption medium at a flow rate of 2BV/h, detecting the lithium content in the effluent, and stopping leaching when the lithium content in the effluent is greater than 0.1ug/L, wherein the resin is in an adsorption saturated state.
S4: and (3) dismantling the resin column subjected to adsorption saturation in the step (S3), soaking in 1mol/L dilute hydrochloric acid, stirring for 5 hours at 25 ℃ in a solid-to-liquid ratio of the resin to the dilute hydrochloric acid of 1:40, and obtaining the lithium-containing solution.
Example 3
S1: discharging and disassembling the lithium battery to obtain positive electrode waste; and adding sodium hydroxide for soaking, and carrying out suction filtration to obtain the anode powder, wherein the liquid-solid ratio of the sodium hydroxide to the anode waste is 10:1.
S2: adding the positive electrode powder obtained in the step S1 into a dilute sulfuric acid solution with the concentration of 0.3mol/L according to the liquid-solid ratio of 30mL to 1g for leaching and extracting lithium, wherein 1mL of 30% hydrogen peroxide is added into the dilute sulfuric acid solution; leaching for 120min at 65 ℃, adjusting the pH value of the system to 8.5, and filtering to obtain leaching liquid and leaching slag.
S3: and (3) allowing the leaching solution to flow through an adsorption column with the crown ether grafted adsorption resin as an adsorption medium at a flow rate of 2BV/h, detecting the lithium content in the effluent, and stopping leaching when the lithium content in the effluent is greater than 0.1ug/L, wherein the resin is in an adsorption saturated state.
S4: and (3) disassembling the resin column subjected to adsorption saturation in the step (S3), immersing in 1mol/L dilute hydrochloric acid, stirring for 6 hours at 25 ℃ in a solid-to-liquid ratio of the resin to the dilute hydrochloric acid of 1:40, and obtaining the lithium-containing solution.
Comparative example 1
The adsorbent resin grafted with crown ether described in this comparative example was prepared as follows
1000G of water phase (10 g of 5% polyvinyl alcohol and the balance of deionized water) is added into a three-port bottle, the mixture is stirred uniformly, the temperature is raised to 40 ℃, the oil phase (the polymerized monomer GMA: TAIC in the oil phase is 5:1, the initiator is azodiisobutyronitrile, the pore-forming agent is n-heptane, the mass ratio of n-heptane to the polymerized monomer is 1:3) is added according to the mass ratio of 3:1 of the water phase to the oil phase, the mixture is stirred at the speed of 260 revolutions per minute, the temperature is raised to 85 ℃ at the speed of 2 ℃/min, the temperature is kept for 4 hours, the mixture is filtered, and the solvent is removed by Soxhlet extraction with petroleum ether as the solvent, and then the resin precursor is obtained.
Mixing 2-hydroxymethyl-12-crown-4 and sodium hydride according to a molar ratio of 1:1, stirring for 6 hours at 55 ℃, stirring under nitrogen atmosphere, adding a resin precursor into the solution, refluxing for 70 hours under nitrogen protection, filtering, washing and drying to obtain the crown-etherified adsorption resin, wherein the mass ratio of the resin precursor to the 2-hydroxymethyl-12-crown-4 is 6:1.
Specific process conditions for recovering lithium element in this comparative example are as follows:
s1: discharging and disassembling the lithium battery to obtain positive electrode waste; adding sodium hydroxide for soaking, and carrying out suction filtration to obtain anode powder, wherein the liquid-solid ratio of the sodium hydroxide to the anode waste is 5:1;
S2: adding the positive electrode powder obtained in the step S1 into a dilute sulfuric acid solution with the concentration of 0.5mol/L according to the liquid-solid ratio of 25mL to 1g for leaching and extracting lithium, wherein 1mL of 30% hydrogen peroxide is added into the dilute sulfuric acid solution; leaching for 200min at 55 ℃, adjusting the pH value of the system to 8.5, and filtering to obtain leaching liquid and leaching slag.
S3: and (3) allowing the leaching solution to flow through an adsorption column adopting the crown-etherified adsorption resin as an adsorption medium at a flow rate of 2BV/h, detecting the lithium content in the effluent, and stopping leaching when the lithium content in the effluent is greater than 0.1ug/L, wherein the resin is in an adsorption saturation state.
S4: and (3) disassembling the resin column subjected to adsorption saturation in the step (S3), immersing in 1mol/L dilute hydrochloric acid, stirring for 5 hours at 25 ℃ in a solid-to-liquid ratio of the resin to the dilute hydrochloric acid of 1:40, and obtaining the lithium-containing solution.
The lithium content and recovery rate related indexes before and after treatment with the crown ether-grafted adsorption resin in examples and comparative examples are shown in the following table:
| examples and comparative examples | Example 1 | Example 2 | Example 3 | Comparative example 1 |
| Lithium content (%) | 38.3 | 36.9 | 38.6 | 36.9 |
| Analysis liquid lithium content (%) | 95.3 | 96.8 | 96.7 | 87.6 |
| Lithium recovery (%) | 95.6 | 98.7 | 97.3 | 88.9 |
As can be seen from the data of the comparative examples and comparative examples, in examples 1 to 3, by grafting 2-hydroxymethyl-12-crown-4 on the precursor resin, through sufficient swelling, the epoxy groups wrapped inside the resin matrix can be fully exposed, and then the epoxy is ring-opened by taking ethylenediamine as a functionalizing agent, a certain amount of amino groups can be introduced on the resin matrix, and hydrogen ions generated when crown ether groups on the resin matrix specifically adsorb lithium can be combined with the amino groups in the resin matrix, so that the adsorption capacity of the resin on lithium ions is further improved; the invention further improves the adsorption capacity and adsorption selectivity of the resin to lithium ions by utilizing the cooperation among crown ether, amino and a specific pore structure in the resin matrix, and the lithium ion resin can obtain high-purity lithium by applying the resin to the lithium element recovery of the positive electrode material of the lithium ion battery, and the recovery rate of the lithium is higher.
Claims (10)
1.A method for extracting lithium from waste electrolyte, comprising the steps of:
S1: discharging and disassembling the lithium battery to obtain positive electrode waste; adding sodium hydroxide for soaking, wherein the liquid-solid ratio of the sodium hydroxide to the positive electrode waste is 3-10:1, and filtering to obtain positive electrode powder;
The active material in the positive electrode waste comprises one or more of LiCoO 2、LiNiO2、LiMnO2;
S2: leaching the positive electrode powder by adopting sulfuric acid with the concentration of 0.3-0.5mol/L and hydrogen peroxide with the concentration of 30%, and filtering to obtain leaching liquid and leaching slag;
s3: allowing the leaching solution to flow through a resin column which adopts the adsorption resin grafted with crown ether as an adsorption medium at the flow rate of 2BV/h, detecting the lithium content in the effluent, and stopping leaching when the lithium content in the effluent is greater than 0.1ug/L, wherein the resin column is in an adsorption saturation state;
the adsorption resin grafted with crown ether is prepared by the following method:
Preparing a resin precursor by using glycidyl methacrylate, triallyl isocyanurate, azodiisobutyronitrile and n-heptane as oil phases, using water and polyvinyl alcohol as water phases and adopting a suspension polymerization mode according to the mass ratio of the water phases to the oil phases being 3:1; adding the resin precursor into a mixed solution of 2-hydroxymethyl-12-crown-4 and sodium hydride, refluxing under nitrogen atmosphere, and drying to obtain crown-etherified adsorption resin; opening the epoxy ring of the crown ether adsorption resin by using ethylenediamine, filtering, cleaning and drying to obtain the adsorption resin grafted with crown ether;
S4: and desorbing the resin by adopting dilute hydrochloric acid to obtain a lithium-containing solution.
2. The method of claim 1, wherein the ratio of sodium hydroxide to positive electrode waste material in step S1 is 10:1.
3. The method for extracting lithium from waste electrolyte as claimed in claim 1, wherein the specific conditions of step S2 are: adding the positive electrode powder obtained in the step S1 into a dilute sulfuric acid solution with the concentration of 0.3-0.5mol/L according to the liquid-solid ratio of 20mL-30mL:1g, leaching and extracting lithium, wherein 1mL of hydrogen peroxide with the concentration of 30% is added into the dilute sulfuric acid solution; leaching at 55-65deg.C for 120-200min, adjusting pH to 8.5, and filtering to obtain leaching solution and leaching residue.
4. The method for extracting lithium from waste electrolyte according to claim 1, wherein in the step S3, the rotation speed of suspension polymerization is 260r/min, the mass ratio of glycidyl methacrylate to triallyl isocyanurate in the oil phase is 5:1, and the mass ratio of n-heptane to glycidyl methacrylate is 1:3.
5. The method for extracting lithium from waste electrolyte as claimed in claim 1, wherein in the step S3, a rate of temperature rise of suspension polymerization is: stirring until the particle size is uniform, heating to 85 ℃ at a speed of 2 ℃/min, and preserving heat for 4h.
6. The method for extracting lithium from waste electrolyte as claimed in claim 1, wherein the crown-etherified adsorbent resin in the step S3 is prepared by the following method:
Mixing 2-hydroxymethyl-12-crown-4 and sodium hydride according to a molar ratio of 1:1 to obtain a mixed solution, stirring at 55 ℃ for 6 hours under a nitrogen atmosphere, adding a resin precursor into the mixed solution, refluxing for 70 hours under the protection of nitrogen with a mass ratio of 6:1, filtering, washing and drying to obtain the crown-etherified adsorption resin.
7. The method for extracting lithium from waste electrolyte as claimed in claim 1, wherein the specific process conditions for ring opening of epoxy by ethylenediamine in step S3 are as follows:
Soaking the crown-etherified adsorption resin in DMF (dimethyl formamide), fully swelling for 24 hours, and obtaining crown-etherified resin according to the mass ratio: ethylenediamine is added in the proportion of 1:5, and the mixture reacts for 5 hours at 70 ℃; and cooling, filtering, washing and airing after the reaction is finished to obtain the adsorption resin grafted with crown ether.
8. The method for extracting lithium from waste electrolyte as claimed in claim 1, wherein the specific process of step S4 is as follows: and (3) disassembling the resin column subjected to adsorption saturation in the step (S3), immersing in 1mol/L dilute hydrochloric acid, stirring for 4-6h at 25 ℃ in a solid-to-liquid ratio of the resin to the dilute hydrochloric acid of 1:36-40, and obtaining the lithium-containing solution.
9. The method of extracting lithium from waste electrolyte as claimed in claim 8, wherein the solid-to-liquid ratio of the resin to the dilute hydrochloric acid is 1:36, and stirring is performed at 25 ℃ for 6 hours.
10. A method for extracting lithium from waste electrolyte and recycling the lithium, which is characterized in that carbonate is added into a lithium-containing solution obtained by the method according to any one of claims 1 to 9 to obtain battery-grade lithium carbonate.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103035977A (en) * | 2013-01-05 | 2013-04-10 | 深圳市泰力废旧电池回收技术有限公司 | Method for separating and recovering lithium from waste lithium ion battery |
| JP2021039933A (en) * | 2019-03-28 | 2021-03-11 | 住友金属鉱山株式会社 | Method for manufacturing positive electrode active material for lithium ion secondary battery |
| CN115747521A (en) * | 2022-12-29 | 2023-03-07 | 江苏电科环保有限公司 | Method for recovering and preparing lithium carbonate from waste lithium ion battery positive electrode material |
| CN118079872A (en) * | 2024-01-16 | 2024-05-28 | 四川智汇新能源有限公司 | Lithium ion specific adsorbent and preparation method and application thereof |
| CN118162119A (en) * | 2024-03-26 | 2024-06-11 | 华东理工大学 | Crown ether modified resin for selectively extracting lithium and preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103035977A (en) * | 2013-01-05 | 2013-04-10 | 深圳市泰力废旧电池回收技术有限公司 | Method for separating and recovering lithium from waste lithium ion battery |
| JP2021039933A (en) * | 2019-03-28 | 2021-03-11 | 住友金属鉱山株式会社 | Method for manufacturing positive electrode active material for lithium ion secondary battery |
| CN115747521A (en) * | 2022-12-29 | 2023-03-07 | 江苏电科环保有限公司 | Method for recovering and preparing lithium carbonate from waste lithium ion battery positive electrode material |
| CN118079872A (en) * | 2024-01-16 | 2024-05-28 | 四川智汇新能源有限公司 | Lithium ion specific adsorbent and preparation method and application thereof |
| CN118162119A (en) * | 2024-03-26 | 2024-06-11 | 华东理工大学 | Crown ether modified resin for selectively extracting lithium and preparation method and application thereof |
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