CN115986251B - Method for removing fluorine in lithium ion battery powder - Google Patents
Method for removing fluorine in lithium ion battery powder Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 67
- 239000011737 fluorine Substances 0.000 title claims abstract description 62
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 62
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 44
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000002002 slurry Substances 0.000 claims abstract description 32
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002699 waste material Substances 0.000 claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- 239000011889 copper foil Substances 0.000 claims abstract description 17
- 239000011888 foil Substances 0.000 claims abstract description 17
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 230000009467 reduction Effects 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 238000002386 leaching Methods 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229940079826 hydrogen sulfite Drugs 0.000 claims description 2
- 238000006115 defluorination reaction Methods 0.000 abstract description 17
- -1 fluorine ions Chemical class 0.000 abstract description 11
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000012066 reaction slurry Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 8
- 239000002243 precursor Substances 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
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- Manufacture And Refinement Of Metals (AREA)
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Abstract
The invention relates to the technical field of lithium ion battery recovery, and particularly discloses a method for removing fluorine in lithium ion battery powder, which comprises the following steps: s1, crushing and separating copper foil and aluminum foil of a waste lithium ion battery to obtain powder; s2, adding pure water into the reaction kettle, adding the powder obtained in the step S1, stirring, slowly adding concentrated sulfuric acid, controlling the final pH value at a preset value, and performing heat treatment; s3, adding pure water into the reaction kettle again, stirring for 30-60min to obtain nickel cobalt manganese lithium slurry, and preparing a low-fluorine ternary solution by using a wet reduction method. Compared with the prior art, the concentration of fluorine ions in the nickel-cobalt-manganese solution prepared from the defluorinated slurry is less than 0.005g/L, the effect of removing the fluorine ions is very good, and meanwhile, after defluorination, the nickel-cobalt-manganese solution avoids corrosion to equipment in the subsequent process flow.
Description
Technical Field
The invention relates to the technical field of lithium ion battery recovery, in particular to a method for removing fluorine in lithium ion battery powder.
Background
The lithium battery has been widely used in the fields of mobile phones, notebook computers, new energy automobiles, etc. because of the advantages of high energy density, long cycle life, no memory effect, high rated voltage, low self-discharge rate, etc.
Along with the rapid development of global economy, the demand for lithium batteries is also increasing, the lithium batteries are composed of positive and negative electrode materials, current collectors, electrolytes, binder PVDF and other components, and fluoride used for modifying the electrolytes, the binder PVDF or the positive electrode materials contains a certain amount of fluorine elements. In the process of recycling and disassembling the waste lithium batteries, due to the existence of the fluorine-containing electrolyte, quantitative fluorine exists in the battery powder, the corrosion performance of the fluorine seriously affects the normal operation of equipment, shortens the service life of the equipment, and affects the quality of preparing a precursor by using the precursor solution obtained by purifying and removing impurities. Fluorine must be removed during wet extraction of nickel cobalt manganese according to the requirements of ternary precursors.
The traditional defluorination process is to extract nickel, cobalt and manganese from waste lithium batteries by using an extracting agent, and then to leave fluorine in the raffinate, and then to input the raffinate into a water treatment workshop for defluorination. However, the fluorine removal is carried out by utilizing an extraction method, the process is complicated, the cost is high, and a certain amount of organic matters remain in the extracted nickel-cobalt-manganese solution, which is unfavorable for preparing the precursor.
Patent CN112079371a discloses a method for recovering fluorine from nickel cobalt manganese solution, which comprises adding fluorine-removing agent into fluorine-containing nickel cobalt manganese solution, adding sodium hydroxide or potassium hydroxide as neutralizing agent at a certain pH, heating and stirring to obtain fluorine-containing filtrate and nickel cobalt manganese filter residue, repeating the above operations for several times, and thus realizing deep impurity removal of F. However, when the concentration of nickel, cobalt and manganese in the leaching solution is too high, the loss rate of nickel, cobalt and manganese is too high due to local overalkaline or entrainment, the working procedure period is long, and a large amount of Na exists in the defluorinated solution + Or K + This can severely degrade the performance of the precursor.
Therefore, how to realize efficient removal of fluoride ions in lithium ion battery waste without corroding equipment is a technical problem that needs to be solved by those skilled in the art.
Disclosure of Invention
The invention aims at: the method for removing fluorine in the lithium ion battery powder aims at solving the technical problems that when waste lithium ion battery materials are recovered by a wet method in the prior art, the content of fluorine ions in a nickel-cobalt-manganese solution is high, a recovered nickel-cobalt-manganese mixture cannot be used for preparing ternary precursors in a large amount, and the fluorine ions in the solution have great corrosiveness to equipment.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for removing fluorine in lithium ion battery powder, comprising the following steps:
s1, crushing and separating copper foil and aluminum foil of a waste lithium ion battery to obtain powder;
s2, adding pure water into the reaction kettle, adding the powder obtained in the step S1, stirring, slowly adding concentrated sulfuric acid, controlling the final pH value, and performing heat treatment;
s3, adding pure water into the reaction kettle again, stirring for 30-60min to obtain nickel cobalt manganese lithium slurry, and preparing a low-fluorine ternary solution by using a wet reduction method.
The preparation method is further improved in that in the step S1, the mass ratio of the concentrated sulfuric acid to the powder is (0.8-1.0): 1. The mass ratio of the concentrated sulfuric acid to the powder is controlled within the range, so that the reaction is ensured to be full and the safety is ensured.
A further improvement of the preparation method according to the invention consists in that in step S1 the concentration of concentrated sulfuric acid is more than 80% by mass, preferably more than 90%.
A further improvement of the preparation method of the invention is that in step S1, the particle size of the powder is smaller than 0.15mm, preferably smaller than 0.1mm. After crushing, the copper foil and the aluminum foil are crushed into fine particles, the powder of the copper foil and the aluminum foil is mainly distributed in the range of >0.3mm, and the active powder of the positive and negative electrodes is mainly concentrated in the range of <0.15 mm. Powder with the diameter smaller than 0.15mm is collected and adopted, and the main purpose is to improve the content of positive and negative active powder in the powder and reduce the doping of impurities. In addition, the surface area of the powder can be increased, so that the contact effect of the powder and concentrated sulfuric acid is better, and the high-efficiency removal of fluoride ions in the waste is ensured.
A further improvement of the preparation method of the invention is that in the step S2, the pH value of the end point is 1-2.5; preferably, the pH is 1.5. Wherein, the control of the pH value is of great importance, and the pH value is controlled within the range, so that fluoride salt can be converted into free hydrofluoric acid, the incomplete conversion can be caused by too large pH value, and the pH value of the subsequent wet reduction solution impurity removal can be influenced by too small pH value.
A further improvement of the preparation method of the invention is that in the step S2, the heat treatment temperature is 120-130 ℃. Because hydrofluoric acid is low-boiling-point acid (boiling point 19.4 ℃), the temperature is easy to remove, and energy is wasted due to the fact that the temperature is too high.
The preparation method is further improved in the step S2, wherein the constant temperature is maintained for 30-120min after the heating to the set temperature in the heat treatment process.
A further improvement of the preparation method of the invention is that in the step S3, the F content in the ternary solution with low fluorine prepared by the wet reduction method is less than or equal to 0.005g/L, preferably the F content is less than or equal to 0.0005g/L.
In step S3, the reducing agent used in the wet reduction method is at least one of sulfur dioxide gas, hydrogen peroxide and sulfite, but not limited to these.
The preparation method is further improved in that in the step S3, the leaching rate of nickel, cobalt and manganese in the nickel, cobalt, manganese and lithium slurry is 30% -35%, and the leaching rate of lithium is 95% -98%.
The invention has the beneficial effects that: according to the method for removing fluorine in lithium ion battery powder, waste lithium ion batteries are crushed, copper foil and aluminum foil are separated to obtain powder, pure water is used as a solvent, concentrated sulfuric acid is added to control the temperature and the pH value for defluorination to obtain nickel-cobalt-manganese-lithium-containing slurry, and the slurry after defluorination is reacted with a reducing agent to completely leach nickel-cobalt-manganese-lithium in the slurry, so that a ternary solution is obtained. The concentration of fluorine ions in the nickel-cobalt-manganese solution prepared from the defluorinated slurry is less than 0.005g/L, the effect of removing the fluorine ions is very good, and meanwhile, after defluorination of the nickel-cobalt-manganese solution, the corrosion to equipment in the subsequent process flow is avoided.
Drawings
Fig. 1 is a process flow diagram of a method of removing fluorine from lithium ion battery powder according to the present invention.
Detailed Description
In order to make the technical solution and advantages of the present invention more apparent, the technical solution of the present invention will be clearly and completely described in conjunction with specific embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A method for removing fluorine in lithium ion battery powder, comprising the following steps:
s1, crushing and separating copper foil and aluminum foil of a waste lithium ion battery to obtain powder with the particle size smaller than 0.15mm;
s2, adding 100ml of pure water into a reaction kettle, adding 100g of the powder obtained in the step S1, stirring, slowly adding 100g of concentrated sulfuric acid with the concentration of 90%, keeping the temperature at 123 ℃ for 45min, and controlling the final pH value to be 1.09;
s3, adding a proper amount of pure water into the reaction kettle again, stirring for 45min to obtain nickel-cobalt-manganese-lithium slurry containing a certain concentration, and then reacting the reaction slurry after defluorination with a reducing agent to completely leach the nickel-cobalt-manganese-lithium in the slurry to obtain a ternary solution. The fluorine F content was found to be 0.004g/L.
Example 2
A method for removing fluorine in lithium ion battery powder, comprising the following steps:
s1, crushing and separating copper foil and aluminum foil of a waste lithium ion battery to obtain powder with the particle size smaller than 0.1 mm;
s2, adding 100ml of pure water into the reaction kettle, adding 100g of the powder obtained in the step S1, stirring, slowly adding 100g of 85% concentrated sulfuric acid, maintaining the temperature at 123 ℃ for 120min, and controlling the final pH value to be 1.55;
s3, adding a proper amount of pure water into the reaction kettle again, stirring for 60min to obtain nickel-cobalt-manganese-lithium slurry containing a certain concentration, and then reacting the reaction slurry after defluorination with a reducing agent to completely leach the nickel-cobalt-manganese-lithium in the slurry to obtain a ternary solution. The fluorine F content was found to be 0.001g/L.
Example 3
A method for removing fluorine in lithium ion battery powder, comprising the following steps:
s1, crushing and separating copper foil and aluminum foil of a waste lithium ion battery to obtain powder with the particle size smaller than 0.15mm;
s2, adding 100ml of pure water into a reaction kettle, adding 100g of the powder obtained in the step S1, stirring, slowly adding 100g of 88% concentrated sulfuric acid, maintaining the temperature at 125 ℃ for 90min, and controlling the final pH value to be 1.81;
s3, adding a proper amount of pure water into the reaction kettle again, stirring for 60min to obtain nickel-cobalt-manganese-lithium slurry containing a certain concentration, and then reacting the reaction slurry after defluorination with a reducing agent to completely leach the nickel-cobalt-manganese-lithium in the slurry to obtain a ternary solution. The fluorine F content was found to be 0.002g/L.
Example 4
A method for removing fluorine in lithium ion battery powder, comprising the following steps:
s1, crushing and separating copper foil and aluminum foil of a waste lithium ion battery to obtain powder with the particle size smaller than 0.15mm;
s2, adding 100ml of pure water into a reaction kettle, adding 100g of the powder obtained in the step S1, stirring, slowly adding 100g of 90% concentrated sulfuric acid, maintaining the temperature at 127 ℃ for 60min, and controlling the final pH value to be 1.31;
s3, adding a proper amount of pure water into the reaction kettle again, stirring for 45min to obtain nickel-cobalt-manganese-lithium slurry containing a certain concentration, and then reacting the reaction slurry after defluorination with a reducing agent to completely leach the nickel-cobalt-manganese-lithium in the slurry to obtain a ternary solution. The fluorine F content was found to be 0.002g/L.
Example 5
A method for removing fluorine in lithium ion battery powder, comprising the following steps:
s1, crushing and separating copper foil and aluminum foil of a waste lithium ion battery to obtain powder with the particle size smaller than 0.15mm;
s2, adding 100ml of pure water into a reaction kettle, adding 100g of the powder obtained in the step S1, stirring, slowly adding 100g of 86% concentrated sulfuric acid, maintaining the temperature at 120 ℃ for 30min, and controlling the final pH value to be 1.88;
s3, adding a proper amount of pure water into the reaction kettle again, stirring for 45min to obtain nickel-cobalt-manganese-lithium slurry containing a certain concentration, and then reacting the reaction slurry after defluorination with a reducing agent to completely leach the nickel-cobalt-manganese-lithium in the slurry to obtain a ternary solution. The fluorine F content was found to be 0.005g/L.
Example 6
A method for removing fluorine in lithium ion battery powder, comprising the following steps:
s1, crushing and separating copper foil and aluminum foil of a waste lithium ion battery to obtain powder with the particle size smaller than 0.15mm;
s2, adding 100ml of pure water into a reaction kettle, adding 100g of the powder obtained in the step S1, stirring, slowly adding 100g of 92% concentrated sulfuric acid, maintaining the temperature at 130 ℃ for 70min, and controlling the final pH value to be 1.38;
s3, adding a proper amount of pure water into the reaction kettle again, stirring for 30min to obtain nickel-cobalt-manganese-lithium slurry containing a certain concentration, and then reacting the reaction slurry after defluorination with a reducing agent to completely leach the nickel-cobalt-manganese-lithium in the slurry to obtain a ternary solution. The fluorine F content was found to be 0.002g/L.
Example 7
A method for removing fluorine in lithium ion battery powder, comprising the following steps:
s1, crushing and separating copper foil and aluminum foil of a waste lithium ion battery to obtain powder with the particle size smaller than 0.15mm;
s2, adding 100ml of pure water into a reaction kettle, adding 100g of the powder obtained in the step S1, stirring, slowly adding 100g of concentrated sulfuric acid with the concentration of 95%, maintaining the temperature at 128 ℃ for 90min, and controlling the final pH value to be 1.0;
s3, adding a proper amount of pure water into the reaction kettle again, stirring for 50min to obtain nickel-cobalt-manganese-lithium slurry containing a certain concentration, and then reacting the reaction slurry after defluorination with a reducing agent to completely leach the nickel-cobalt-manganese-lithium in the slurry to obtain a ternary solution. The fluorine F content was found to be 0.004g/L.
Example 8
A method for removing fluorine in lithium ion battery powder, comprising the following steps:
s1, crushing and separating copper foil and aluminum foil of a waste lithium ion battery to obtain powder with the particle size smaller than 0.15mm;
s2, adding 100ml of pure water into a reaction kettle, adding 100g of the powder obtained in the step S1, stirring, slowly adding 100g of 80% concentrated sulfuric acid, maintaining the temperature at 123 ℃ for 75min, and controlling the final pH value to be 2.5;
s3, adding a proper amount of pure water into the reaction kettle again, stirring for 60min to obtain nickel-cobalt-manganese-lithium slurry containing a certain concentration, and then reacting the reaction slurry after defluorination with a reducing agent to completely leach the nickel-cobalt-manganese-lithium in the slurry to obtain a ternary solution. The fluorine F content was found to be 0.003g/L.
Example 9
A method for removing fluorine in lithium ion battery powder, comprising the following steps:
s1, crushing and separating copper foil and aluminum foil of a waste lithium ion battery to obtain powder with the particle size smaller than 0.1 mm;
s2, adding 100ml of pure water into a reaction kettle, adding 100g of the powder obtained in the step S1, stirring, slowly adding 100g of concentrated sulfuric acid with the concentration of 95%, preserving heat for 100min at the temperature of 90 ℃, and controlling the final pH value to be 1.5;
s3, adding a proper amount of pure water into the reaction kettle again, stirring for 45min to obtain nickel-cobalt-manganese-lithium slurry containing a certain concentration, and then reacting the reaction slurry after defluorination with a reducing agent to completely leach the nickel-cobalt-manganese-lithium in the slurry to obtain a ternary solution. The fluorine F content was found to be 0.0005g/L.
Comparative example 1
A method for removing fluorine in lithium ion battery powder, comprising the following steps:
s1, crushing and separating copper foil and aluminum foil of a waste lithium ion battery to obtain powder with the particle size smaller than 0.15mm;
s2, adding 100ml of pure water into a reaction kettle, adding 100g of the powder obtained in the step S1, stirring, slowly adding a proper amount of concentrated sulfuric acid, maintaining the temperature at 126 ℃ for 50min, and controlling the final pH value to be 2.61;
s3, adding a proper amount of pure water into the reaction kettle again, stirring for 45min to obtain nickel-cobalt-manganese-lithium slurry containing a certain concentration, and reacting the reaction slurry after defluorination with a reducing agent to completely leach the nickel-cobalt-manganese-lithium in the slurry to obtain a ternary solution. The fluorine F content was found to be 0.01g/L.
Comparative example 2
A method for removing fluorine in lithium ion battery powder, comprising the following steps:
s1, crushing and separating copper foil and aluminum foil of a waste lithium ion battery to obtain powder with the particle size smaller than 0.15mm;
s2, adding 100ml of pure water into a reaction kettle, adding 100g of the powder obtained in the step S1, stirring, slowly adding a proper amount of concentrated sulfuric acid, maintaining the temperature at 150 ℃ for 25min, and controlling the final pH value to be 2.58;
s3, adding a proper amount of pure water into the reaction kettle again, stirring for 60min to obtain nickel-cobalt-manganese-lithium slurry containing a certain concentration, and then reacting the reaction slurry after defluorination with a reducing agent to completely leach the nickel-cobalt-manganese-lithium in the slurry to obtain a ternary solution. The fluorine F content was found to be 0.025g/L.
The fluorine content test of the nickel cobalt manganese lithium ternary solutions obtained in examples 1 to 9 and comparative examples 1 to 2 is shown in the following table:
from the test results of comparative examples 1-2 and examples 1-9, when the heat treatment temperature was controlled to be 120-130 ℃ and the holding time was controlled to be 30-120min and the ph=1-2.5, the fluorine content of examples 1-8 was less than 0.005g/L in the ternary solution obtained by wet reduction, and the fluorine removal efficiency was higher than that of comparative examples 1-2. In particular, when the pH is controlled to 1.5, the fluorine removal effect is excellent, and the fluorine F content in the ternary solution after wet reduction is 0.0005g/L. By the method provided by the invention, the fluoride ions in the waste lithium ion batteries can be effectively removed, so that the content of the fluoride ions is lower, and further, the corrosion to equipment in the subsequent wet reduction process is avoided.
Variations and modifications of the above embodiments will occur to those skilled in the art to which the invention pertains from the foregoing disclosure and teachings. Therefore, the present invention is not limited to the above-described embodiments, but is intended to be capable of modification, substitution or variation in light thereof, which will be apparent to those skilled in the art in light of the present teachings. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.
Claims (6)
1. The method for removing fluorine in the lithium ion battery powder is characterized by comprising the following steps of:
s1, crushing and separating copper foil and aluminum foil of a waste lithium ion battery to obtain powder;
s2, adding pure water into the reaction kettle, adding the powder obtained in the step S1, stirring, slowly adding concentrated sulfuric acid, controlling the final pH value at a preset value, and performing heat treatment;
s3, adding pure water into the reaction kettle again, stirring for 30-60min to obtain nickel cobalt manganese lithium slurry, and preparing a low-fluorine nickel cobalt manganese lithium ternary solution by using a wet reduction method;
in the step S1, the particle size of the powder is smaller than 0.15mm; in the step S2, the pH value of the end point is 1-2.5;
in the step S2, the heat treatment temperature is 120-130 ℃; in the step S2, after heating to the set temperature in the heat treatment process, the constant temperature is maintained for 30-120min.
2. The method for removing fluorine from lithium ion battery powder according to claim 1, wherein in step S1, the mass ratio of concentrated sulfuric acid to powder is (0.8-1.0): 1.
3. The method for removing fluorine from lithium ion battery powder according to claim 1, wherein in the step S1, the mass percentage concentration of the concentrated sulfuric acid is greater than 80%.
4. The method for removing fluorine in lithium ion battery powder according to claim 1, wherein in the step S3, the F content in the nickel-cobalt-manganese-lithium ternary solution with low fluorine prepared by the wet reduction method is less than or equal to 0.005g/L.
5. The method for removing fluorine from lithium ion battery powder according to claim 1, wherein in step S3, the leaching rate of nickel cobalt manganese in the nickel cobalt manganese lithium slurry is 30% -35%, and the leaching rate of lithium is 95-98%.
6. The method for removing fluorine in lithium ion battery powder according to claim 1, wherein in step S3, the reducing agent used in the wet reduction method is at least one of sulfur dioxide gas, hydrogen peroxide and sulfite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310027010.3A CN115986251B (en) | 2023-01-09 | 2023-01-09 | Method for removing fluorine in lithium ion battery powder |
Applications Claiming Priority (1)
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