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WO2025118990A1 - Procédé et système de broyage, de tri et de recyclage de batteries au lithium-ion usagées - Google Patents

Procédé et système de broyage, de tri et de recyclage de batteries au lithium-ion usagées Download PDF

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Publication number
WO2025118990A1
WO2025118990A1 PCT/CN2024/133531 CN2024133531W WO2025118990A1 WO 2025118990 A1 WO2025118990 A1 WO 2025118990A1 CN 2024133531 W CN2024133531 W CN 2024133531W WO 2025118990 A1 WO2025118990 A1 WO 2025118990A1
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Prior art keywords
solid
crushing
black powder
condensing
screening
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Chinese (zh)
Inventor
魏文添
刘雅婷
韩恒
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Guangzhou Tinci Materials Technology Co Ltd
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Guangzhou Tinci Materials Technology Co Ltd
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides
    • 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

Definitions

  • the present application relates to the field of new energy, and specifically to a method and system for crushing, sorting and recycling waste lithium-ion batteries.
  • Waste lithium-ion batteries are mainly composed of shell, positive electrode, negative electrode, diaphragm and electrolyte.
  • the current mainstream recycling process is to crush the waste lithium-ion batteries under a protective atmosphere for multi-level physical sorting, and sort out the shell, diaphragm, positive and negative electrode powder, copper and aluminum particles (powder) for recycling.
  • Prior art such as CN114914570A, discloses a method for recycling waste lithium-ion battery electrolyte, which removes the solvent by low-temperature heating and then separates the shell, diaphragm, etc.; however, in actual production, we found that it is very difficult to use a one-time separation method to separate the shell and diaphragm; at the same time, although the binder in the positive electrode material on the electrode sheet is carbonized after pyrolysis, the efficiency of separating black powder is still very low.
  • the technical problem solved in this case is: how to recover black powder efficiently and with high purity.
  • the main purpose of the present application is to provide a method for crushing, sorting and recycling waste lithium-ion batteries, which can efficiently recycle black powder with high purity.
  • the present application can also realize the graded recovery of black powder while realizing the recovery of black powder, and at the same time make the diaphragm easier to remove.
  • the application also provides a system for implementing the method.
  • a method for crushing, sorting and recycling waste lithium-ion batteries comprises the following steps:
  • Step 1 After the lithium-ion battery is crushed, it is heated to 60-150° C. under the protection of an inert gas to volatilize at least part of the solvent in the electrolyte to obtain a first solid;
  • Step 2 removing the battery shell in the first solid to obtain a second solid
  • Step 3 Screening the second solid to obtain a first undersize and a first oversize, wherein the first undersize contains free black powder in the second solid;
  • Step 4 removing the membrane from the first screened material through airflow sorting to obtain a third solid
  • Step 5 Pyrolyzing the first undersize and the third solid to decompose the lithium salt and crack and carbonize the binder on the pole piece and the diaphragm to obtain a fourth solid;
  • Step 6 Screening the fourth solid to obtain a second undersize material and a second oversize material; the second undersize material is the first black powder;
  • Step 7 Crush the second oversize material, and sieve the crushed product to obtain a third undersize material and a third oversize material; the third undersize material is the second black powder, and the third oversize material is the metal substrate particles of the electrode.
  • the black powder recovery is optimized from the last step of the traditional technology to black powder screening recovery before diaphragm sorting, black powder screening recovery after pole piece pyrolysis, and black powder screening recovery after pole piece crushing; this design maximizes the recovery rate of black powder, graded recovery of black powder, and high-purity recovery of black powder;
  • the binder on the electrode is decomposed, the bonding strength between the black powder and the electrode is weakened, and the black powder is dry and brittle.
  • the screening process of the electrode some black powder will fall off. In this step, the recovery efficiency of black powder is improved through pyrolysis and screening.
  • the black powder obtained by screening before diaphragm sorting and after pyrolysis of the pole piece has relatively few metal impurities and relatively high purity. Through pyrolysis combined with screening before diaphragm sorting and screening after pyrolysis, efficient and high-purity recovery of black powder is achieved;
  • the black powder on the electrode is fully knocked off and crushed into powder during the crushing process.
  • the black powder and metal substrate particles can be screened out; however, due to the existence of the electrode crushing step, the metal impurities in this part of the black powder are relatively high, but the overall proportion of black powder is small, so it is beneficial to carry out targeted treatment of the above two black powders of different purities in hydrometallurgy.
  • the present application first heats to volatilize the solvent, then removes the shell, then screens, and finally removes the diaphragm, which can reduce the difficulty of diaphragm airflow sorting and the airflow sorting wind force, thereby reducing the probability of black powder being drawn away;
  • removing the outer shell first creates favorable conditions for subsequent screening. If the outer shell is not removed, the outer shell in the solid is heavier and accounts for a relatively large volume, and its squeezing of the diaphragm can easily cause the outer shell to move with the diaphragm in the screen, causing a large amount of black powder to accumulate in the outer shell. The accumulation of black powder forces the subsequent airflow sorting to be forced to increase, and the black powder will be further carried away by the airflow, reducing the recovery rate of the black powder.
  • step 2 specifically includes: removing the battery shell in the first solid by airflow sorting process, and the second solid enters step 3 by negative pressure extraction.
  • the sieve aperture of step 3 is 2-50 mesh; the sieve aperture of step 6 is 80-150 mesh; and the sieve aperture of step 7 is 80-150 mesh.
  • the sieve aperture of step 3 can be selected as: 2, 5, 10, 15, 20, 25, 30, 40 or 50 mesh;
  • the sieve aperture of step 6 can be selected as: 80, 85, 90, 95, 100, 110, 120, 130, 140 or 150 mesh;
  • the sieve aperture of step 7 can be selected as: 80, 85, 90, 95, 100, 110, 120, 130, 140 or 150 mesh;
  • the screening mesh number of step 3 in the present application is 2 to 50 meshes.
  • the free black powder accounts for a relatively high proportion and is mixed with the pole piece and the fluffy diaphragm.
  • the smaller the screening mesh number, such as 2 meshes the higher the separation efficiency of the free black powder and the more thorough the screening, so as to avoid the loss of black powder caused by the airflow being drawn away in the next step.
  • the size of the diaphragm in the crushed mixture is generally larger than the size of the shell and the pole piece.
  • this step will not cause the diaphragm to be screened down and mixed with the first screened material.
  • a lower screening mesh is more conducive to the complete separation of the free black powder, thereby reducing the loss of black powder and improving its recovery rate and the airflow sorting efficiency of the diaphragm.
  • the first screen undersize and/or the third solid enters step 5 after magnetic separation.
  • step 1 is specifically:
  • the battery Under a protective atmosphere, the battery is cut and destroyed, and the materials after cutting and destruction are crushed, the size of the crushed materials is controlled to be 10-30mm, and the battery components are completely broken up.
  • the size of the crushed material can be controlled to 10 mm, 15 mm, 20 mm, 25 mm or 30 mm;
  • the heating time is 30 to 120 minutes
  • the boiling points of the solvents are: ethylene carbonate 240°C; propylene carbonate 242°C; dimethyl carbonate 90°C; diethyl carbonate 126-128°C; ethyl methyl carbonate 107°C; ethyl acetate 77°C; propyl propionate 136°C; propyl acetate 102°C;
  • the solvent evaporation temperature can be preferably selected to be 100-150°C; if 100°C is selected, it is recommended to maintain the system at negative pressure to further reduce the boiling point of the solvent. In the above process, the solvent with a boiling point above 150°C is generally evaporated and enters step 2.
  • the heating temperature is 100°C, ethyl acetate and dimethyl carbonate will volatilize; if the heating temperature is 110°C, propyl acetate and ethyl methyl carbonate will volatilize; if the heating temperature is 150°C, diethyl carbonate and propyl propionate will volatilize;
  • the lowest temperature can be as low as 60°C, which can make the low boiling point solvent evaporate.
  • the solvent evaporation temperature can be preferably selected to be 110 to 140°C;
  • the solvent volatilization temperature can be selected to be 70, 80, 85, 90, 95, 100, 110, 120, 130, 140 or 150°C;
  • the pyrolysis temperature in step 5 is 300-550° C. and the time is 30-120 min.
  • the pyrolysis temperature is 330-500°C; more preferably 350-450°C;
  • the pyrolysis temperature may be selected to be 300, 350, 400, 450, 500 or 550°C;
  • step 1 a first gas is also obtained, and the solvent is recovered by condensing the first gas;
  • step 5 a second gas is obtained after pyrolysis, and PF 5 in the second gas is recovered by multi-stage condensation.
  • the present application also discloses a system for implementing any of the methods described above, comprising a first crushing unit for crushing lithium-ion batteries, a heating device for heating and volatilizing the solvent in the crushed lithium-ion batteries, a first separation device for removing the battery shell in the first solid, a first screening device for screening the second solid to remove free black powder in the second solid, a second separation device for removing the diaphragm in the first screened material, a pyrolysis device for pyrolyzing the first screened material and the third solid, a second screening device for screening the fourth solid, a second crushing unit for crushing the second screened material, and a third screening device for screening the crushed product of the second crushing unit.
  • a magnetic separation device is further provided between the second separation device and the pyrolysis device;
  • the first crushing unit includes a shredding device for cutting off the complete lithium-ion battery and a crushing device for crushing the shredded lithium-ion battery;
  • the first separation device and the second separation device are both airflow separators; the second solid is the light component separated by the first separation device; the third solid is the heavy component separated by the second separation device;
  • the first screening device and the second screening device are both drum screens.
  • it further includes a first condensation unit and a second condensation unit, and the gas generated in the heating device is transported to the first condensation unit through a pipeline; the gas generated in the pyrolysis device is transported to the second condensation unit through a pipeline.
  • the pyrolysis device performs pyrolysis in two steps; the temperature of the first pyrolysis is 200-300°C; the temperature of the second pyrolysis is 300-500°C.
  • the second condensing unit comprises a pre-condensing device for condensing the gas generated by the first pyrolysis, a primary condensing device for condensing the uncondensed gas of the pre-condensing device, a secondary condensing device for condensing the uncondensed gas of the primary condensing device, and a tertiary condensing device for condensing the uncondensed gas of the secondary condensing device, which are connected in sequence;
  • the first condensing unit comprises a primary condensing device for condensing the gas generated in the heating device and a separation device for separating fluorine-containing compounds from the tail gas of the primary condensing device; the gas separated by the separation device is sent to a secondary condensing device for condensation.
  • the shell and the diaphragm are sequentially sorted after the electrolyte is evaporated at low temperature, so as to prevent the shell and the diaphragm soaked by the electrolyte from adhering to and taking away a small amount of black powder during sorting;
  • the shell and free black powder should be screened out in turn before the separation membrane to avoid the loss of black powder caused by the black powder being taken away together with the membrane during separation.
  • the shell should not be removed, which will cause the membrane to be squeezed by the shell during screening and be difficult to separate, thus reducing the efficiency of black powder recovery.
  • pyrolysis of the first screened material and the pole piece can pyrolyze the organic matter in the black powder, improve the purity of the black powder, and reduce the adhesion of the black powder on the pole piece, making the black powder on the pole piece dry and brittle, making the black powder easier to fall off during the screening operation after pyrolysis, thereby improving the recovery rate and purity of the black powder;
  • the electrode size is reduced by crushing again, and the black powder on the positive and negative electrode sheets is easier to fall off and crush into powder.
  • the separation of black powder and copper and aluminum particles can be more thorough, and the recovery of black powder containing metal powder impurities is realized.
  • the present application realizes black powder grading by collecting black powder before and after crushing, which is conducive to targeted treatment of black powder of different levels.
  • FIG1 is a pipeline flow chart of Example 1
  • FIG2 is a pipeline flow chart of Example 5.
  • FIG3 is a pipeline flow chart of Example 6
  • FIG4 is a pipeline flow chart of Example 4.
  • FIG1 it specifically includes the following devices: a first crushing unit for crushing lithium-ion batteries, a heating device 2 for heating at least part of the solvent in the crushed lithium-ion batteries to a volatilization temperature, a first separation device 3 for removing the battery shell in the first solid, a first screening device 4 for screening the second solid to remove free black powder in the second solid, a second separation device 5 for removing the diaphragm in the first screened material, a pyrolysis device 6 for pyrolyzing the first screened material and the third solid, a second screening device 7 for screening the fourth solid, a second crushing unit 8 for crushing the second screened material, and screening the crushed product of the second crushing unit.
  • a first crushing unit for crushing lithium-ion batteries
  • a heating device 2 for heating at least part of the solvent in the crushed lithium-ion batteries to a volatilization temperature
  • a first separation device 3 for removing the battery shell in the first solid
  • a first screening device 4 for screening the second solid to remove free black powder
  • a third screening device 9 is provided, and a magnetic separation device 10 is further provided between the second separation device and the pyrolysis device;
  • the first crushing unit comprises a shredding device 1 for cutting off the complete lithium-ion battery and a crushing device 11 for crushing the shredded lithium-ion battery;
  • the first separation device and the second separation device are both airflow separators;
  • the second solid is the light component separated by the first separation device;
  • the third solid is the heavy component separated by the second separation device, and the light component and the heavy component mentioned in this application refer to the components drawn away by the airflow during the airflow separation process, namely the light component, and the components not drawn away by the airflow are the heavy components;
  • the first screening device and the second screening device are both drum screens.
  • Step 1 crushing 1 ton of cylindrical waste lithium iron phosphate batteries using a first crushing unit under nitrogen protection, and heating to the solvent volatilization temperature of the electrolyte under inert gas protection to obtain a first solid;
  • the main organic solvents of the electrolyte are: ethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC), with a mass ratio of 3:1:6;
  • the lithium salt is lithium hexafluorophosphate, accounting for 13% of the weight of the electrolyte;
  • the active material of the positive electrode is lithium iron phosphate, and the current collector is on carbon-coated aluminum foil; the mass ratio of lithium iron phosphate, conductive agent SuperP, adhesive PVDF and carbon nanotubes (CNT) on the current collector is 95.8:1:2.5:0.7;
  • the crushing is carried out by a tearing device and a crushing device.
  • the battery is first torn into pieces and invalidated by a tearing device, and then crushed by a hammer crushing device.
  • the size after crushing is 10 to 30 mm.
  • a mixture of shell, diaphragm, pole piece, electrolyte, and free black powder is obtained.
  • the mixture is heated by a heating device (100°C, 1h) to volatilize the solvent in the electrolyte.
  • the first solid remaining after volatilization is the shell, diaphragm, pole piece, lithium salt, black powder and some non-volatile additives.
  • the first solid-liquid mixture also contains a high-boiling organic solvent.
  • the oxygen content is controlled to be less than 2.0% to avoid the risk of explosion.
  • the effective countermeasure is to continuously introduce nitrogen as a protective gas. At the same time, nitrogen is introduced into the heating device throughout the process to facilitate solvent volatilization.
  • Step 2 using a first separation device to remove the battery shell in the first solid to obtain a second solid;
  • the first solid is sent to the first separation device, which is a wind separator, and the diaphragm, the electrode, the lithium salt and some non-volatile additives, high-boiling organic solvents, etc. are sucked into the first screening device by negative pressure extraction; wherein the additives and high-boiling organic solvents mainly enter the first screening device in the form of adhering to the diaphragm and the electrode;
  • Step 3 Screening the second solid with a first screening device to obtain a first undersize and a first oversize, wherein the first undersize contains free black powder in the second solid and a high-boiling organic solvent infiltrated in the black powder;
  • the sieve aperture of the first sieve device is 10 mesh
  • the aperture of the screen should be set larger, that is, the mesh number should be smaller.
  • more than 50% of the black powder needs to be screened out in this step. If the free black powder cannot be screened out completely, part of it will be drawn out in step 4. At the same time, if a large amount of black powder cannot be screened out in this step, then in step 4, it will make it difficult for the diaphragm to be drawn out.
  • the first screening device in this step is a drum screen
  • Step 4 remove the diaphragm from the first sieve material through air flow sorting to obtain a third solid; the third solid is treated by a magnetic separation device to remove the magnetic metal powder before entering step 5;
  • first undersize material may also enter the magnetic separation device together with the third solid
  • This step is carried out by a second separation device, which is an airflow separator, and the membrane is sucked away by the airflow separator; the remaining is the third solid; more specifically, the first screen material is placed on a 80-100 mesh screen conveyor belt, on which is an airflow separator;
  • Step 5 Pyrolyzing the first undersize and the third solid to decompose the lithium salt and crack the electrode binder to obtain a fourth solid;
  • the pyrolysis temperature of the pyrolysis device is 500° C., and the time is 1.5 h. During the pyrolysis process, nitrogen protection is introduced, and the oxygen content is controlled to be less than 2.0%.
  • the key point of this step is that: through pyrolysis, not only the decomposition of lithium salt is achieved to avoid the presence of lithium salt in the black powder, but also the binder is cracked, so that the black powder on the electrode falls off during the screening process in step 6, and more black powder with higher purity is obtained; the most important thing is: through pyrolysis, the organic matter in the black powder screened in step 6 is fully decomposed to improve the purity of the black powder.
  • Step 6 Screening the fourth solid to obtain a second undersize material and a second oversize material; the second undersize material is the first black powder;
  • This step is performed by a second screening device, which is a 120-mesh drum screen.
  • the first black powder collected has a low impurity metal content, thereby reducing the difficulty of extracting lithium and other positive electrode metal materials from the black powder and improving its purity.
  • Step 7 The second screened material is crushed by a second crushing unit, and the crushed product is screened by a third screening device of 120 mesh to obtain a third screened material and a third screened material; the third screened material is the second black powder, and the third screened material is the metal substrate particles of the electrode.
  • the size of the crushed particles is 1 to 3 mm;
  • the crushing process is indispensable in this step, because after repeated experiments, if the crushing is not performed, the size of the pole piece is still too large. Although there is no binder on the pole piece, it is still difficult to completely separate the black powder from the pole piece.
  • the size of the pole piece is reduced, which is conducive to the black powder falling off the pole piece; on the other hand, the friction and impact caused by the crushing can accelerate the falling of the black powder and crush it into powder, which is conducive to subsequent screening.
  • the pole piece is not crushed but directly screened, after analyzing the pole piece on the sieve, it was found that it contained black powder entrainment equivalent to 10 to 20wt% of the total black powder. Therefore, crushing before screening is very necessary.
  • the second black powder obtained in this step should not be mixed with the first black powder; the above crushing operation will produce more metal powder, which will increase the difficulty of black powder recovery and treatment. It is impossible to separate the metal powder by simple screening and other operations. It is necessary to specially recover the aluminum and copper elements to achieve the purpose of recovering the black powder with a higher purity. This part of black powder accounts for about 5-20% of the total amount of black powder. Although the operation steps and processes are increased when recovering this part of black powder, it can further improve the purity and recovery rate of black powder, which is a necessary operation.
  • step 1 if the crushing size in step 1 is adjusted to the size in step 7, the size of the electrode piece is reduced from the source, but at the same time, the diaphragm is over-crushed.
  • the diaphragm with too small size will increase the difficulty of diaphragm sorting in step 4.
  • Some small-sized diaphragms will be buried by the electrode pieces or other solids and difficult to be extracted.
  • excessive crushing in step 1 causes the screened material obtained by screening in step 3 to contain small-sized electrode pieces and diaphragms, making the subsequent processes more complicated.
  • the shell and diaphragm are sorted after the electrolyte is evaporated at low temperature to prevent the shell and diaphragm soaked in electrolyte from adhering to and taking away a small amount of black powder during sorting;
  • the shell and free black powder are screened out in turn before the diaphragm is sorted to prevent the black powder from being taken away during the diaphragm sorting and causing black powder loss, and to avoid the problem that the diaphragm is squeezed by the shell during screening and difficult to separate due to the shell not being removed;
  • the first screen under material and the pole piece are pyrolyzed to pyrolyze the organic matter in the black powder and improve the purity of the black powder , and at the same time reduce the adhesion of the black powder on the electrode, making the black powder on the electrode dry and crisp, so that the black powder is easier to fall off the electrode during the screening operation after pyrolysis, thereby improving the purity and recovery rate of the black powder;
  • the crushing size of step 1 should not be too small.
  • the crushing size of step 1 is related to the screening aperture of step 2. If the crushing size of step 1 is too small, the screening mesh of step 2 must be large, which will increase the difficulty of black powder screening, resulting in part of the black powder being sucked away along with the diaphragm during the subsequent diaphragm removal process; therefore, the crushing size of step 1 and the crushing size of step 7 should be reasonably set and coordinated to achieve process optimization;
  • the crushing in step 7 is of great significance to the full screening of black powder, and the crushing in this step is indispensable.
  • step 7 The amount of black powder collected in step 7 is relatively small. For this part of black powder, multiple batches of black powder in step 7 should be mixed and processed uniformly. At the same time, it should be processed separately from the black powder collected in step 6. This can effectively reduce the process difficulty of black powder processing in step 6.
  • the method is substantially the same as that of Example 1, except that the battery in step 1 is cut off and the damaged material is crushed, and the size of the crushed material is controlled to be 10 to 20 mm;
  • the heating temperature for volatilizing the solvent in step 1 is 150° C. and the time is 2 h;
  • the mesh number of the first screening device is 50 mesh; the mesh number of the second screening device is 80 mesh; the mesh number of the third screening device is 150 mesh;
  • step 5 the pyrolysis temperature is 300° C. and the time is 2 h.
  • the method is substantially the same as that of Example 1, except that the battery in step 1 is cut off and the damaged material is crushed, and the size of the crushed material is controlled to be 20 to 30 mm;
  • the heating temperature for evaporating the solvent in step 1 is 60° C., the system is kept under negative pressure, and the time is 2 h;
  • the mesh number of the first screening device is 2 meshes; the mesh number of the second screening device is 150 meshes; the mesh number of the third screening device is 80 meshes;
  • step 5 the pyrolysis temperature is 550° C. and the time is 0.5 h.
  • step 3 is eliminated; after step 2 is completed, the second solid is directly sent to step 4 for airflow sorting to remove the diaphragm.
  • the method is substantially the same as Example 1, except that step 6 is omitted and the fourth solid is directly sent to step 7 for crushing.
  • the method is generally the same as Example 1, except that there is no crushing operation in step 7, and the second screened material is directly screened again.
  • the high-temperature cracking temperature is too low, it will lead to incomplete decomposition of adhesives, etc., and incomplete shedding of black powder during the subsequent crushing and sorting process, resulting in a low black powder recovery rate. Therefore, selecting a high-temperature cracking process and setting a suitable processing temperature are factors that need to be considered in the process of optimizing the process.
  • the estimated theoretical content of black powder in 1 ton of cylindrical waste lithium iron phosphate batteries is about 530 kg. Since it cannot be guaranteed that every battery in the waste batteries is exactly the same, but the basic component contents of batteries of the same model are similar, the data in Table 1 above are only used as a basis for inferring data trends, and are not used as error-free results for specific recovery rates.
  • This embodiment mainly introduces the use of the method of the present application to recover black powder from a square aluminum shell ternary battery
  • the positive electrode material of the ternary battery is: nickel-cobalt-manganese ternary material, with the chemical formula of LiNi 0.5 Mn 0.3 Co 0.2 O 2 ;
  • the main organic solvents of the electrolyte are: ethylene carbonate, propylene carbonate, ethyl methyl carbonate, and diethyl carbonate, and the mass ratio of the four is 25:5:15:55;
  • the lithium salt is lithium hexafluorophosphate, with a content of 12.5wt%;
  • the active material of the positive electrode is a ternary material (chemical formula: LiNi 0.5 Mn 0.3 Co 0.2 O 2 ), and the current collector is a carbon-coated aluminum foil; the mass ratio of the ternary material, the conductive agent SuperP, and the adhesive PVDF on the current collector is 96.8:2:1.2;
  • FIG. 4 The flowchart of this embodiment refers to FIG. 4 , which is different from FIG. 1 in that the first undersize material enters the magnetic separation device 10 for magnetic separation; the specific steps of the recovery operation are:
  • Step 1 crushing 1 ton of square aluminum shell ternary battery under nitrogen protection, and heating under inert gas protection to volatilize the electrolyte solvent to obtain a first solid;
  • the battery is shredded and invalidated by the shredding device 1 and then shredded by the shredding device 11.
  • the shredding device 1 is a hammer-type shredding device, and the size of the shredded battery is 10-30 mm.
  • a mixture of a shell, a diaphragm, a pole piece, an electrolyte, and free black powder is obtained.
  • the mixture is heated by a heating device 2 (120° C., 1.5 h) to volatilize the electrolyte solvent.
  • the first solid remaining after volatilization is the shell, the diaphragm, the pole piece, the lithium salt, the black powder, and some non-volatile additives and high-boiling solvents.
  • the oxygen content is controlled to be less than 2.0% to avoid the risk of combustion and explosion.
  • the effective countermeasure is to continuously introduce nitrogen as a protective gas. At the same time, nitrogen is introduced into the heating device throughout the process to facilitate the volatilization of the solvent.
  • Step 2 removing the battery shell in the first solid to obtain a second solid
  • the first solid is sent to the first separation device 3, which is a wind separator, and the diaphragm, the electrode, the lithium salt, and some non-volatile additives, high-boiling organic solvents, etc. are sucked into the first screening device 4 by negative pressure extraction; wherein the additives and high-boiling organic solvents mainly enter the first screening device 4 in the form of adhering to the diaphragm and the electrode;
  • Step 3 Screening the second solid to obtain a first undersize and a first oversize, wherein the first undersize contains free black powder in the second solid and a high-boiling organic solvent soaked in the black powder;
  • This step is carried out in the first screening device 4, and the screening aperture is 10 mesh;
  • the first screening device 4 in this step is a drum screen
  • Step 4 remove the diaphragm from the first sieve material through air flow sorting to obtain a third solid; the first sieve material and the third solid are separated by a magnetic separation device to remove the magnetic metal powder and then enter step 5;
  • This step is carried out by the second separation device 5, which is an airflow separator, and the membrane is sucked away by the airflow separator; the remaining is the third solid; more specifically, the first screen material is placed on a 100-mesh screen conveyor belt, on which is the airflow separator;
  • Step 5 Pyrolyzing the first undersize and the third solid to decompose the lithium salt and crack the electrode binder to obtain a fourth solid;
  • the pyrolysis temperature of the pyrolysis device 6 is 500° C., and the time is 1.5 h. During the pyrolysis process, nitrogen protection is introduced, and the oxygen content is controlled to be less than 2.0%.
  • Step 6 Screening the fourth solid to obtain a second undersize material and a second oversize material; the second undersize material is the first black powder;
  • This step is performed by the second screening device 7, which is a drum screen with a mesh number of 120.
  • the first black powder collected has a low impurity metal content, so it is easier to extract lithium and other positive electrode material metal elements from the black powder;
  • Step 7 The second screened material is crushed by a second crushing unit 8, and the crushed product is screened by a third screening device 9 with a mesh size of 120 to obtain a third screened material and a third screened material; the third screened material is the second black powder, and the third screened material is the metal substrate particles of the electrode.
  • the crushed size is 1 to 3 mm.
  • the black powder recovery rate reached more than 98%, indicating that this solution is also applicable to the treatment of waste square aluminum shell ternary batteries and other types of batteries.
  • the first part mainly describes the collection of black powder, and next, the treatment of tail gas after the pyrolysis operation in step 5 is mainly explained.
  • Example 1 only the step 5 is introduced to obtain solid, and the method for treating the tail gas is not clearly stated.
  • the first method is to directly treat it harmlessly and then discharge it, and the second method is to recover the resources and then discharge it. Both methods have their own advantages.
  • the former has low processing costs and has a relatively mature process for implementation; the latter is complicated to process, but renewable resources can be recovered.
  • This embodiment mainly introduces the process of discharging after harmless treatment.
  • FIG2 specifically includes a de-oiling device 12, a tail gas combustion device 13, a heat exchanger 14, a flue gas quenching tower 15, a semi-dry reactor 16, a dust collector 17, an induced draft fan 18, a primary alkali spray tower 19, and a secondary alkali spray tower 20 connected in sequence.
  • the tail gas is tested to be qualified, it is discharged from a chimney 21;
  • the oil removal device 12 is connected to the flue gas outlet of the pyrolysis device;
  • the heating device 2 is connected to an exhaust fan and a primary condensing device 22.
  • the exhaust fan is used to condense the organic solvent volatilized by heating the heating device 2.
  • the condensation is preferably performed using cold water at about 5°C.
  • the primary condensing device 22 is preferably a tubular condenser.
  • step 1 the volatilization temperature is not high, and the highest does not exceed 150°C. Then there will be some high-boiling organic solvents, and the boiling points of these high-boiling organic solvents reach above 150°C.
  • the boiling point of unsaturated carbonate is very high. If it is treated at a volatilization temperature of 100°C, many solvents cannot be volatilized. These solvents are collectively referred to as high-boiling organic solvents, that is, solvents with boiling points above the set volatilization temperature; these solvents will become the first screen underproducts as they are treated in step 3;
  • the objects of pyrolysis are the first screen undersize and the third solid, which specifically include: high boiling organic solvent, lithium salt, black powder, pole piece, binder and other substances attached to the positive electrode material;
  • the pyrolysis temperature reaches 500°C
  • the high-boiling organic solvent will evaporate, the lithium salt will decompose into LiF and PF 5 , the binder on the electrode will decompose into carbon and fluorine-containing gas, and a small part of the binder will decompose into low-molecular pyrolysis products;
  • the pyrolysis process is a process of continuously discharging the exhaust gas in the furnace. Therefore, it is unrealistic to ensure that all high-boiling organic solvents and binders are completely decomposed.
  • the resulting problem is that thick oil stains will form on the pipeline between the smoke exhaust position and the exhaust gas combustion device 13.
  • an oil removal device 12 is set between the smoke exhaust position and the exhaust gas combustion device 13;
  • the oil removal device 12 may be selected as a filter, an electrostatic oil remover containing an electrostatic plate electric field, etc.;
  • the flue gas generated by the pyrolysis device 6 enters the heat exchanger 14 for heat exchange to reduce energy consumption after passing through the deoiling device 12, and then enters the tail gas combustion device 13 for combustion.
  • the natural gas ignition combustion system begins to assist combustion and temperature increase. When the temperature in the furnace reaches the set temperature, the mixed exhaust gas begins to enter the furnace. According to the three T principles of combustion (temperature, time, and vortex), the waste and combustion-supporting air are burned by high-temperature pyrolysis in the furnace. The residence time is sufficient and the combustion efficiency is above 99.99%, ensuring that the organic matter is fully oxidized and decomposed.
  • the flue gas stays in the furnace for a sufficient time to be fully burned, and the waste is completely decomposed into acidic gases such as CO 2 and H 2 O at high temperatures.
  • the ash produced by the incineration is packed and sent to the ash storage room by forklift, and then transported by car to a qualified unit for treatment as required.
  • the temperature of the TO furnace (pyrolysis gas combustion chamber) is maintained at >1100°C under auxiliary fuel, making the incineration more complete and achieving the effect of smokeless, odorless and no secondary pollution.
  • the flue gas stays in the secondary incineration chamber for 2 seconds, so that the trace organic matter and dioxins in the flue gas can be fully decomposed.
  • the decomposition efficiency exceeds 99.99%, ensuring that the hazardous waste entering the incineration system is fully burned.
  • the high-temperature flue gas after incineration passes through the heat exchanger 14 and enters the flue gas quenching tower 15 to be rapidly cooled to 200° C. to avoid the generation of dioxins.
  • the flue gas is pushed by the induced draft fan 18 to enter the primary alkali spray tower 19 and the secondary alkali spray tower 20 to purify and absorb the acidic gas, and then discharged through the chimney 21.
  • PF 5 in the cracked gas is hydrolyzed to produce HF and H 3 PO 4 acidic gases, which are neutralized, precipitated, purified and absorbed through water washing, alkali washing and other processes.
  • the alkali liquid spray tower is added with the reagent NaOH, and the wastewater of the waste gas water washing treatment system is neutralized with Ca(OH) 2 , and finally CaF 2 and Ca 3 (PO 4 ) 2 precipitation are generated, which are outsourced for treatment after dehydration.
  • step 5 is divided into two steps, including step 51 and step 52 which are performed successively;
  • Step 51 Under the protection of inert gas, the first screen undersize and the third solid are subjected to a first pyrolysis to decompose the lithium salt and volatilize the high-boiling organic solvent, and the products of this part are recycled;
  • Step 52 Under the protection of inert gas, the solid material after pyrolysis in step 51 is subjected to a second pyrolysis, and the second pyrolysis is used to carbonize the binder; the tail gas from the second pyrolysis is directly harmlessly treated and then discharged.
  • the harmless treatment can refer to the traditional treatment method of the relevant tail gas in Example 5.
  • the temperature of the first pyrolysis is 200-300°C; the temperature of the second pyrolysis is 300-500°C;
  • the equipment supporting step 51 is a pre-condensing device 23 for condensing the gas generated by the first pyrolysis, a primary condensing device 24 for condensing the uncondensed gas of the pre-condensing device, a secondary condensing device 25 for condensing the uncondensed gas of the primary condensing device, and a tertiary condensing device 26 for condensing the uncondensed gas of the secondary condensing device, which are connected in sequence;
  • the pre-condensing device 23, the primary condensing device 24, the secondary condensing device 25, and the tertiary condensing device 26 are all tubular condensers;
  • Step 510 The gas generated by the first pyrolysis contains high-boiling organic solvent, low-molecular cracking products after cracking of the binder, nitrogen, water, PF 5 , HF, and POF 3 ;
  • Step 511 The gas obtained in step 510 is sent to the pre-condensing device 23 to remove high-boiling organic solvents and low-molecular cracking products therein; the pre-condensing device 23 is a water-cooled tubular condenser, and cooling water at 0 to 5° C. is passed into the pre-condensing device.
  • the uncondensed gas discharged from the pre-condensing device is the first gas.
  • Step 512 Send the first gas to the primary condensing device 24, which is a tubular condenser.
  • the refrigerant of the primary condensing device is frozen brine.
  • the temperature of the frozen brine is -5°C to 0°C.
  • HF and water are fully condensed to obtain a second gas.
  • the second gas contains only nitrogen, PF 5 , POF 3 and trace amounts of unidentified impurities.
  • the refrigerant temperature in the tubular condenser should be significantly lower than the boiling point of the object to be condensed, and can even be close to the freezing point of the object. The reason is that the amount of nitrogen in the first gas is relatively large and the gas flow rate is relatively fast. If the condensation temperature is too high, the object to be condensed will not be fully condensed.
  • Step 513 Send the second gas to the secondary condensation device 25 for condensation to obtain the third gas;
  • the secondary condensation device 25 is a tubular condenser, the refrigerant used is liquid nitrogen, and the condensation temperature is -60 to -50°C; this step is mainly used to remove POF 3 ;
  • Step 514 Send the third gas to the three-stage condensation device 26 for condensation to collect liquid PF 5 .
  • the three-stage condensation device 26 is a tubular condenser, and the refrigerant used is liquid nitrogen.
  • the condensation temperature is -120 to -110°C.
  • the above embodiment 1 records that most of the solvent is volatilized at the solvent volatilization temperature.
  • a small amount of lithium hexafluorophosphate or other lithium salts still has the risk of decomposition, which also leads to a small amount of PF 5 being generated after the solvent is recovered in step 1;
  • step 1 If the PF 5 in the solvent recovery process of step 1 is not further recovered and processed, it will not only cause environmental pollution but also waste resources;
  • a primary condensing device 22 for condensing the gas generated in step 1 and a separation device for separating the fluorine-containing compound from the tail gas of the primary condensing device;
  • the separation device is a cold trap 27;
  • the primary condensing device 22 condenses the volatilized solvent in step 1 at a temperature of 0 to 5°C, and is a water-cooled tubular condenser; the uncondensed gas discharged from the primary condensing device 22 is introduced into a cold trap 27 using -20°C supercooled brine as a refrigerant to obtain a fourth gas, which is a relatively pure fluorine-containing gas; the main purpose of the cold trap 27 is to fully remove the uncondensed organic solvent to prevent the organic solvent from entering step 513 and causing trouble to the condensation process of step 513.
  • the fourth gas contains a large amount of nitrogen and fluorine-containing gas, which is sent to step 513, mixed with the second gas, and sent to the secondary condensation device 25 for condensation;
  • the use of cold traps can effectively prevent PF 5 from spilling into the atmosphere and can effectively recover PF 5 .

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Abstract

La présente demande, qui appartient au domaine des nouvelles énergies, divulgue un procédé de broyage, de tri et de recyclage de batteries au lithium-ion usagées, comprenant les étapes suivantes : étape 1, le broyage d'une batterie au lithium-ion et le chauffage, pour obtenir un premier matériau solide ; étape 2, le retrait d'un boîtier, pour obtenir un deuxième matériau solide ; étape 3, le tamisage du deuxième matériau solide, pour obtenir un premier produit de dimensions inférieures et un premier produit de dimensions supérieures ; étape 4, la réalisation d'un tri par flux d'air sur le premier produit de dimensions supérieures pour éliminer un séparateur, pour obtenir un troisième matériau solide ; étape 5, la pyrolyse du premier produit de dimensions inférieures et du troisième matériau solide, pour obtenir un quatrième matériau solide ; étape 6, le tamisage du quatrième matériau solide, pour obtenir un deuxième produit de dimensions inférieures et un deuxième produit de dimensions supérieures ; et étape 7, le broyage et le tamisage du deuxième produit de dimensions supérieures, pour obtenir un troisième produit de dimensions inférieures et un troisième produit de dimensions supérieures. Au moyen de la collecte de poudre noire avant et après le broyage à l'étape 7, le présent procédé met en œuvre une gradation de poudre noire, ce qui facilite le traitement ciblé de poudre noire de différentes qualités. Le taux de récupération de poudre noire et l'efficacité de collecte de la présente demande sont élevés, et un séparateur est efficacement éliminé. En outre, la présente demande divulgue également un système approprié pour ledit procédé.
PCT/CN2024/133531 2023-12-05 2024-11-21 Procédé et système de broyage, de tri et de recyclage de batteries au lithium-ion usagées Pending WO2025118990A1 (fr)

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