CN115747499A - Method for recovering lithium from waste lithium ion battery - Google Patents
Method for recovering lithium from waste lithium ion battery Download PDFInfo
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- CN115747499A CN115747499A CN202211704332.9A CN202211704332A CN115747499A CN 115747499 A CN115747499 A CN 115747499A CN 202211704332 A CN202211704332 A CN 202211704332A CN 115747499 A CN115747499 A CN 115747499A
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The application provides a method for recovering lithium from waste lithium ion batteries, which can avoid the generation of toxic gas, has simple and safe treatment process, convenient operation and low disposal cost, effectively ensures the production safety and the personal health, can obtain organic acid salt while preparing lithium fluoride, and effectively improves the recovery utilization rate of resources; the method comprises the following steps of 1) adding a positive electrode material obtained by disassembling a waste lithium ion battery into an organic acid solution, stirring at a high temperature, and filtering to obtain a first filtrate; 2) Concentrating the first filtrate, adding a fluoride salt solution, stirring at a high temperature, filtering to obtain a second filtrate, and drying a filter cake to obtain industrial-grade lithium fluoride; 3) And concentrating and crystallizing the second filtrate, and drying to obtain the organic acid salt.
Description
Technical Field
The application relates to the technical field of industrial solid waste treatment, in particular to a method for recovering lithium from waste lithium ion batteries.
Background
The lithium ion battery is widely applied to the fields of mobile electronics, communication and the like due to the advantages of high energy density, high charging rate, long cycle life and the like, the development of the new energy industry of the lithium battery is accelerated by the requirement of green and environment-friendly energy, the use amount of the lithium battery is increased year by year, but the cycle life of the lithium ion battery is usually short and is generally 5~8 years, when the service life of the battery is used up, a large amount of scrapped lithium ion batteries can be generated, if the lithium ion battery is not recycled, not only can the metal in the battery pollute the land, but also can the waste of precious metal in the lithium battery, the value of cyclic utilization is lost, and economic loss is caused.
Currently, a hydrometallurgical process is mainly adopted for recycling the lithium ion battery anode material, inorganic acid such as strong acid including sulfuric acid, nitric acid, hydrochloric acid and the like is used for leaching the anode material, then a precipitator is used for classifying and recycling various metals, however, the inorganic acid is used for leaching, toxic gas is generated, production safety and human health are damaged, and the hydrometallurgical process is usually used for recycling and preparing lithium carbonate and is less used for preparing lithium fluoride with higher value; lithium fluoride has very important function in industrial production, can be used for traditional trades such as glass, ceramics, rare earth smelting, etc., and is used in fields such as new energy, new material and new medicine, etc., the existing preparation of lithium fluoride usually adopts the reaction of lithium salt with higher purity and hydrofluoric acid solution, but hydrofluoric acid has strong corrosivity and permeability, influence the safety in utilization, the invention patent CN103073031A discloses a method for preparing lithium fluoride by phosphate fertilizer by-product sodium fluoride, through adding sodium hydroxide solution into phosphate fertilizer by-product sodium fluoride, filtering after heating and stirring, washing, purifying to obtain sodium fluoride, then adding water and heating, adding lithium hydroxide solution, filtering after the stirring reaction is finished, washing the precipitate with distilled water until the washing liquid is neutral, drying to obtain lithium fluoride finished product, the method uses by-product sodium fluoride to prepare lithium fluoride, not only needs lithium hydroxide with higher price as auxiliary material, causes the increase of process disposal cost, but also is difficult to be used for the treatment of waste lithium ion battery containing multiple metallic elements.
Disclosure of Invention
The method for recovering lithium from the waste lithium ion battery can avoid the generation of toxic gas, is simple and safe in treatment process, convenient to operate and low in treatment cost, effectively ensures production safety and personal health, can obtain organic acid salt while preparing lithium fluoride, and effectively improves the recovery rate of resources.
The technical scheme is as follows: a method for recovering lithium from waste lithium ion batteries is characterized in that: which comprises the following steps of,
1) Adding the anode material obtained by disassembling the waste lithium ion battery into an organic acid solution, stirring at a high temperature, and filtering to obtain a first filtrate;
2) Concentrating the first filtrate, adding a fluoride salt solution, stirring at a high temperature, filtering to obtain a second filtrate, and drying a filter cake to obtain industrial-grade lithium fluoride;
3) And concentrating and crystallizing the second filtrate, and drying to obtain the organic acid salt.
It is further characterized in that:
in the step 1), the organic acid solution is salicylic acid, oxalic acid, acetic acid or citric acid, the concentration of the organic acid solution is 0.1 to 1mol/L, and the liquid-solid ratio of the organic acid solution to the anode material is 10 to 40mL/g;
in the step 1), stirring at the temperature of 80-100 ℃ for 1-3h;
in the step 2), the lithium ion concentration of the concentrated solution is 20 to 40g/L, the fluoride salt solution is a saturated sodium fluoride, potassium fluoride, ammonium fluoride or ammonium bifluoride solution, and the molar ratio of the fluoride salt to the lithium ion is 1 to 1.1;
in the step 2), stirring at the temperature of 80-100 ℃ for 1-2h; the drying temperature of the filter cake is 100 to 120 ℃, and the drying time is 3 to 5 hours;
in the step 3), the second filtrate is subjected to a reduced pressure concentration crystallization mode, the evaporation temperature is 70-90 ℃, the pressure is-0.2 Mpa-0.8 Mpa, the drying temperature is 100-120 ℃, and the drying time is 2-4 h;
the anode material after the waste lithium ion battery is disassembled contains lithium and one or more of nickel, cobalt and manganese.
The beneficial effect of this application is:
1. the application uses the organic acid as the leaching agent, can avoid producing toxic gas, ensures the production safety and the physical health of operators, uses the fluoride salt as the precipitating agent, and is relatively convenient to add and safe to operate.
2. According to the method, organic acid is used as a leaching agent, nickel, cobalt and manganese in the lithium ion battery positive electrode material are complexed with the organic acid to generate precipitates, organic acid lithium salt exists in a solution due to high solubility, the filtrate obtained after precipitation and filtration is concentrated and then saturated fluoride salt is added to be used as a precipitating agent, and lithium fluoride has high solubility (0.27 g/100 gH) 2 O) is much less than the solubility of lithium organate (6.12 g/100 gH) 2 O), the organic acid lithium can be converted into lithium fluoride with higher price, and the lithium fluoride with higher purity is finally obtained, so that the recycling value of the lithium ion battery is improved.
3. The method has the advantages of simple treatment process and convenience in operation, not only can obtain high purity lithium fluoride, but also can obtain a byproduct organic acid salt with higher purity, simultaneously reduces the cost of auxiliary materials, fully utilizes the anode material obtained after the disassembly of the solid waste lithium ion battery and added organic acid, fluoride salt and other substances, and further effectively improves the recycling rate of resources.
Drawings
Fig. 1 is a schematic process flow diagram of the present application.
Detailed Description
The present application is further described with reference to the accompanying drawings, figure 1, and the examples below:
example 1
Adding 2g of anode material obtained after the disassembly of the waste lithium ion battery into 80mL of 0.1mol/L oxalic acid solution, stirring for 1h at 80 ℃, filtering, concentrating the first filtrate until the concentration of lithium ions is 20g/L, adding saturated sodium fluoride solution with the theoretical value of 1 time of the lithium ions, stirring for 1h at 80 ℃, and filtering, wherein the generated chemical reaction formula is as follows:
and drying the filter cake at 100 ℃ for 5h to obtain a lithium fluoride product with the mass fraction of 98.5%.
Concentrating and crystallizing the obtained second filtrate at 70 deg.C under-0.8 Mpa, drying at 100 deg.C for 4 hr to obtain sodium oxalate byproduct with sodium oxalate content of 99.15%, and can be used for processing cellulose finishing agent, textile, leather, etc.
Example 2
2g of anode material obtained after the disassembly of the waste lithium ion battery is added into 50mL of 0.5mol/L salicylic acid solution, stirred for 2 hours at 90 ℃ and filtered. And concentrating the first filtrate until the concentration of lithium ions is 30g/L, adding a saturated potassium fluoride solution with the theoretical value of 1.05 times of the lithium ions, stirring at 90 ℃ for 1.5h, filtering, and drying a filter cake at 110 ℃ for 4h to obtain a lithium fluoride product with the mass fraction of 98.2%.
Concentrating and crystallizing the obtained second filtrate at 80 deg.C under-0.5 Mpa, drying at 110 deg.C for 3 hr to obtain potassium salicylate byproduct with potassium salicylate content of 98.54%, which can be used as dye intermediate, disinfectant, food antiseptic, etc.
Example 3
2g of anode material obtained after the disassembly of the waste lithium ion battery is added into 20mL of 1mol/L citric acid solution, stirred for 3 hours at the temperature of 100 ℃, and then filtered. And concentrating the first filtrate until the concentration of lithium ions is 40g/L, adding a saturated ammonium fluoride solution with the theoretical value of 1.1 times of the lithium ions, stirring at 100 ℃ for 1 hour, filtering, and drying the filter cake at 120 ℃ for 3 hours to obtain a lithium fluoride product with the mass fraction of 98.1%.
Concentrating and crystallizing the obtained second filtrate at 90 deg.C under-0.2 Mpa, drying at 120 deg.C for 2 hr to obtain ammonium citrate byproduct, wherein the ammonium citrate content is 98.12%, and can be used as ceramic dispersant, permeation promoter, detergent raw material, and soil conditioner component, and also can be used in medicine, electronic industry, etc.
Table one: GB/T22666-2008 lithium fluoride standard and example comparison table
LiF-1, liF-2, liF-3 respectively represent first-class products, second-class products and third-class products in the GB/T22666-2008 lithium fluoride standard, the impurity content of the product lithium fluoride obtained in the embodiment 1~3 meets the requirement of the first-class products, and the lithium fluoride content meets the requirement of the second-class products in the GB/T22666-2008 lithium fluoride standard.
Claims (7)
1. A method for recovering lithium from waste lithium ion batteries is characterized in that: which comprises the following steps of,
1) Adding the anode material obtained by disassembling the waste lithium ion battery into an organic acid solution, stirring at a high temperature, and filtering to obtain a first filtrate;
2) Concentrating the first filtrate, adding a fluoride salt solution, stirring at a high temperature, filtering to obtain a second filtrate, and drying a filter cake to obtain industrial-grade lithium fluoride;
3) And concentrating and crystallizing the second filtrate, and drying to obtain the organic acid salt.
2. The method for recovering lithium from waste lithium ion batteries according to claim 1, wherein the method comprises the following steps: in the step 1), the organic acid solution is salicylic acid, oxalic acid, acetic acid or citric acid, the concentration of the organic acid solution is 0.1 to 1mol/L, and the liquid-solid ratio of the organic acid solution to the anode material is 10 to 40mL/g.
3. The method for recovering lithium from waste lithium ion batteries according to claim 1, wherein the method comprises the following steps: in the step 1), the stirring temperature is 80-100 ℃, and the stirring time is 1-3 h.
4. The method for recovering lithium from waste lithium ion batteries according to claim 1, wherein the method comprises the following steps: in the step 2), the concentration of lithium ions in the concentrated solution is 20-40g/L, the fluoride salt solution is a saturated sodium fluoride, potassium fluoride, ammonium fluoride or ammonium bifluoride solution, and the molar ratio of the fluoride salt to the lithium ions is 1-1.1.
5. The method for recovering lithium from waste lithium ion batteries according to claim 1, wherein the method comprises the following steps: in the step 2), stirring at the temperature of 80-100 ℃ for 1-2h; the drying temperature of the filter cake is 100 to 120 ℃, and the drying time is 3 to 5 hours.
6. The method for recovering lithium from waste lithium ion batteries according to claim 1, wherein the method comprises the following steps: in the step 3), the second filtrate is subjected to a reduced pressure concentration crystallization mode, the evaporation temperature is 70-90 ℃, the pressure is-0.2-0.8 Mpa, the drying temperature is 100-120 ℃, and the drying time is 2-4 h.
7. The method for recovering lithium from waste lithium ion batteries according to claim 1, wherein the method comprises the following steps: the anode material after the waste lithium ion battery is disassembled contains lithium and one or more of nickel, cobalt and manganese.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116770075A (en) * | 2023-05-11 | 2023-09-19 | 广东工业大学 | Application of reductive acid leaching system in leaching recovery of waste lithium ion battery components |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116770075A (en) * | 2023-05-11 | 2023-09-19 | 广东工业大学 | Application of reductive acid leaching system in leaching recovery of waste lithium ion battery components |
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