CN112225191A - Method for degrading PVDF in positive electrode of waste lithium iron phosphate battery - Google Patents
Method for degrading PVDF in positive electrode of waste lithium iron phosphate battery Download PDFInfo
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- ZTOZIUYGNMLJES-UHFFFAOYSA-K [Li+].[C+4].[Fe+2].[O-]P([O-])([O-])=O Chemical compound [Li+].[C+4].[Fe+2].[O-]P([O-])([O-])=O ZTOZIUYGNMLJES-UHFFFAOYSA-K 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
-
- 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
Abstract
The invention provides a method for degrading PVDF in a positive electrode of a waste lithium iron phosphate battery. The method adopts a three-step combined process of primary sintering, airflow classification and secondary sintering, achieves the purposes of stripping the lithium iron phosphate powder and completely degrading PVDF into a carbon material by the combination and cooperation of sintering processes of different temperature sections and airflow classification processes, effectively avoids the corrosion damage of hydrogen fluoride generated by the failure of PVDF on lithium iron phosphate powder particles, and also avoids the integrity damage of the original powder structure. The method has wide application range, is suitable for most of the existing equipment and industrial batch production, meets the requirements of energy conservation, simplicity and environmental protection, provides a new process for stripping the powder recovered from the lithium battery anode material, and has huge application prospect and economic value.
Description
Technical Field
The invention relates to the technical field of recovery and treatment of anode materials of waste lithium batteries, in particular to a method for degrading PVDF in anodes of waste lithium iron phosphate batteries.
Background
Due to the fact that energy problems are more prominent, countries all over the world are dedicated to research and develop new energy, and a plurality of new energy sources are continuously appeared on the background, wherein the research and development of lithium iron phosphate batteries are important progresses in the battery industry. According to the statistical prediction of China Battery alliance and China center for automobile technology research, the global power battery demand is 41.6 GW.h in 2016, wherein the demand of the lithium iron phosphate power battery reaches 23.9 GW.h, which occupies 57.4% of the market, and the accumulated scrappage of the power batteries of pure electric passenger vehicles and hybrid power passenger vehicles in China reaches 12-17 million tons by 2020. If the waste lithium iron phosphate batteries are not treated in time, the environment can be seriously polluted, and a large amount of metal resources can be wasted, so that the waste lithium iron phosphate batteries need to be recycled for protecting the environment and realizing the comprehensive utilization of resources, and the method has important significance for the sustainable development of the whole industry.
At present, the recovery of the anode material of the waste lithium iron phosphate battery is mainly based on lithium iron phosphate, and aiming at the process of recovering and recycling the lithium iron phosphate material, a wet method and a solid-phase high-temperature calcination method are mainly adopted for separating lithium iron phosphate powder, and the wet method process is most commonly performed by NMP soaking and strong acid cooking, but the processes can cause environmental pollution and have lower economic ratio. Compared with wet recovery, the solid-phase high-temperature calcination method has the characteristics of simple operation, short flow and large-scale application. However, at present, researches on the degradation degree of the binder PVDF in the recycled material obtained by the solid phase method and the influence of substances such as carbon materials generated by carbonizing the binder PVDF at high temperature on the electrochemical performance of the lithium iron phosphate powder are relatively few.
The invention patent with the application number of CN111003700A discloses a method for recycling waste lithium iron phosphate batteries. Firstly, calcining the waste lithium iron phosphate battery at high temperature of 650 ℃ in a closed inert atmosphere for 0.5-6h, and then crushing, screening, magnetically separating and air-flow separating to obtain carbon powder and lithium iron phosphate fine powder; then adding an iron source, a phosphorus source, a lithium source and an additive for grinding and mixing; and finally, placing the mixture in an inert atmosphere for high-temperature sintering at the temperature of 650-800 ℃ for 4-20h to obtain the lithium iron phosphate carbon composite material. However, this method has the following disadvantages: 1) the method is characterized in that the method is used for directly calcining a battery comprising a lithium iron phosphate positive electrode, a graphite negative electrode, a diaphragm and a structural component, so that the mixing and dismantling of positive and negative electrode powder and impurities are difficult; 2) the temperature of the primary calcination is too high, so that the decomposition of PVDF can generate a large amount of HF (hydrogen fluoride), corrode the surface of the material, equipment and pollute the environment; 3) the temperature of the secondary calcination is too high, so that the olivine structure crystal of the lithium iron phosphate material becomes large, and the subsequent processing procedure and the electrochemical performance of the material are influenced; 4) in addition, various added source materials and additives have small effects on removing PVDF and purifying lithium iron phosphate materials, so that certain resource waste is caused.
The invention patent with the publication number of CN106636649A provides a method for recycling lithium iron phosphate anode materials of waste lithium batteries. Firstly, carrying out high-temperature baking under inert gas at 480 ℃ of 350-; then, ultrasonic or mechanical friction is adopted, deionized water or ethanol is used for washing, all the residual anode materials on the pole piece are desorbed, all the anode materials are collected after filtration, the sample is dried, and the sample is ground; then, adding a carbon source into the sample obtained in the second step, and performing ball milling to enable the material to reach the required particle size; secondly, under the inert gas, the sample milled in the third step is baked at high temperature again at 800 ℃ for 4-24 h; and finally, the sample re-baked in the fourth step can be directly used as a material for manufacturing a new battery pole piece. However, this method has the following disadvantages: 1) the roasting temperature of 350-480 ℃ under inert gas is too high, so that a large amount of HF (hydrogen fluoride) is generated by the decomposition of PVDF, and the surface of a material, equipment and the environment are corroded; 2) the liquid cleaning and drying procedures after the powder separation have low economic benefit; 3) in addition, the added carbon source has small effects on removing PVDF and purifying the lithium iron phosphate material, so that certain resource waste is caused; 4) the temperature of the secondary calcination at 600-800 ℃ is too high, which causes the olivine structure crystal of the lithium iron phosphate material to be enlarged, and the subsequent process and electrochemical performance of the material are affected.
The invention patent with publication number CN104362408B discloses a method for recycling lithium iron phosphate waste in the manufacturing process of lithium iron phosphate batteries. Placing the pole piece to be recovered in a muffle furnace, baking at the high temperature of 400-600 ℃ for 2-3 h, decomposing the binder to lose efficacy, and completely removing active material lithium iron phosphate and conductive agent powder from the current collector aluminum foil; putting the powder in the previous step into a muffle furnace, baking the powder at the high temperature of 650-800 ℃ for 4-6 hours, and sieving the powder to obtain lithium iron phosphate powder; filtering, washing the lithium iron phosphate powder by using deionized water, and adding an ethanol wetting agent after washing to prepare a suspension; mixing soluble lithium salt, iron salt and phosphate in an ethanol solution according to a ratio, adding the mixture into the suspension, mixing, and performing vacuum drying at 120-140 ℃; roasting for 3-6 hours at the temperature of 850 ℃ under the atmosphere of inert gas of 650-. However, this method has the following disadvantages: 1) the temperature of the primary calcination is too high, so that the decomposition of PVDF can generate a large amount of HF (hydrogen fluoride), corrode the surface of the material, equipment and pollute the environment; 2) the temperature of the secondary calcination is too high, so that the olivine structure crystal of the lithium iron phosphate material becomes large, and the subsequent processing procedure and the electrochemical performance of the material are influenced; 3) in addition, various added source materials and additives have small effects on removing PVDF and purifying lithium iron phosphate materials, so that certain resource waste is caused, and the economic benefit is low.
In view of the above, there is a need to design an improved method for degrading PVDF in the positive electrode of waste lithium iron phosphate batteries to solve the above problems.
Disclosure of Invention
The invention aims to provide a method for degrading PVDF in a positive electrode of a waste lithium iron phosphate battery.
In order to realize the aim, the invention provides a method for degrading PVDF in the anode of a waste lithium iron phosphate battery, which comprises the following steps:
s1, firstly, cleaning and coarsely crushing the waste lithium iron phosphate battery positive pole piece obtained through disassembly, then, placing the coarsely crushed positive pole piece with a preset size in a calcining device in an inert gas atmosphere, heating to 320-360 ℃ at a preset first heating rate, carrying out calcining treatment for 1-4 h, completing primary sintering, and obtaining positive pole piece powder after PVDF fails;
s2, performing air classification treatment on the positive pole piece powder with the failed PVDF obtained in the step S1 to obtain positive pole piece powder with a preset particle size;
and S3, placing the cathode powder obtained in the step S2 in a calcining device in an inert gas atmosphere, heating to 500-650 ℃ at a preset second heating rate, calcining for 0.25-4 h, completing secondary sintering, and completely carbonizing and degrading the invalid PVDF to obtain the lithium iron phosphate powder with completely degraded PVDF.
As a further improvement of the invention, in step S1, the size of the coarsely crushed pole piece is 1-10 mm.
As a further improvement of the invention, the calcining equipment comprises but is not limited to one of a rotary kiln, a roller kiln, a tubular furnace and a muffle furnace.
As a further improvement of the invention, in step S2, after the air classification treatment, the grain size of the positive powder is 5-80 μm.
In a further improvement of the present invention, in step S1, the first temperature increase rate is 1 to 10 ℃/min.
As a further improvement of the invention, the inert gas is flowing gas, and the flowing speed is 0.05-10L/min.
As a further improvement of the invention, the inert gas includes but is not limited to one or more of nitrogen, argon and helium.
As a further improvement of the invention, the PVDF comprises but is not limited to one or more of PVDF5130 series and HSV900 series.
In a further improvement of the present invention, in step S3, the second temperature increase rate is 1 to 10 ℃/min.
As a further improvement of the present invention, in the primary sintering process of step S1, the PVDF is cracked, and the cracked product is small-molecule organic hydrocarbons; in the secondary sintering process described in step S3, the PVDF that has failed is completely degraded and carbonized into a carbon material.
The invention has the beneficial effects that:
1. the method for degrading the PVDF in the anode of the waste lithium iron phosphate battery adopts a combined process of primary sintering, airflow grading and secondary sintering, so that on one hand, the temperature of a large amount of fluorine-containing gas generated by PVDF decomposition failure is avoided, and the technical defect that in the prior art, the lithium iron phosphate powder particles are corroded and damaged by hydrogen fluoride gas generated by PVDF failure is effectively avoided; on the other hand, the thermal decomposition data of PVDF is reasonably utilized, the characteristic of excessive high-temperature growth of lithium iron phosphate finished product crystals is effectively avoided, PVDF is completely removed as far as possible, and the technical defects that in the prior art, the lithium iron phosphate crystals are excessively grown to influence the electrochemical performance and are not beneficial to the subsequent high-temperature storage and cycle performance of the full battery due to overhigh calcination temperature are overcome.
The purposes of stripping the lithium iron phosphate powder and completely degrading PVDF into a carbon material are achieved through the combination and cooperation of sintering processes at different temperature sections and air flow grading processes, and meanwhile, the integrity of the original powder structure is effectively prevented from being damaged. The process has wide application range, is suitable for most of the existing equipment and industrial batch production, meets the requirements of energy conservation, simplicity and environmental protection, provides a new process for stripping the powder recovered from the lithium battery anode material, and has huge application prospect.
2. The method for degrading PVDF in the anode of the waste lithium iron phosphate battery, provided by the invention, has the following combined mechanism in the combined process of primary sintering, airflow classification and secondary sintering:
firstly, the primary sintering process is carried out at the temperature of 320-; meanwhile, PVDF can be disabled, so that the lithium iron phosphate pole piece powder and PVDF are effectively stripped; meanwhile, the flowing inert gas reaction atmosphere has the following functions: in certain calcining equipment, the space is limited, different temperatures correspond to different gas flow rates, decomposition products can be discharged better in time without influencing the reaction process of the whole powder, and gas can be saved to the maximum degree.
And then, an air flow grading process aims at screening and grading a small amount of aluminum scraps and lithium iron phosphate powder after the PVDF fails and the lithium iron phosphate pole piece powder is effectively stripped, and simultaneously, the aim of crushing the lithium iron phosphate powder can be achieved.
Finally, the secondary sintering process is carried out at 650 ℃ under flowing inert gas, so that the failed PVDF is completely carbonized, and the temperature range is obtained according to the PVDF thermal decomposition data; the secondary sintering process effectively overcomes the technical defects that in the prior art, PVDF cannot be completely carbonized when the calcination temperature is lower than 500 ℃, or lithium iron phosphate crystals excessively grow to influence the electrochemical performance and be not beneficial to the high-temperature storage and cycle performance of a subsequent full battery when the calcination temperature is higher than 650 ℃.
Therefore, the three processes are combined, different sintering temperatures are reasonably set according to thermogravimetric analysis of PVDF and detection of decomposition products at different temperature sections, and the powder stripping of the lithium iron phosphate pole piece and the complete degradation of PVDF in the lithium iron phosphate pole piece are realized by utilizing the segmented temperature sintering process, so that the method is green and environment-friendly and has certain economic value. The technical defects of environmental pollution and low economy caused by the fact that a wet process (such as NMP soaking and strong acid cooking) is adopted for powder separation of the lithium iron phosphate pole piece in the prior art are effectively overcome.
Drawings
Fig. 1 is a schematic flow chart of the method for degrading PVDF in the positive electrode of the waste lithium iron phosphate battery provided by the invention.
FIG. 2 is a thermogravimetric TG analysis of PVDF.
Fig. 3 is a content reduction ratio curve diagram of PVDF in the lithium iron phosphate positive electrode sheet at different calcination temperatures.
FIG. 4 is a graph of the reduction ratio of pure PVDF at different calcination temperatures.
Fig. 5 is a graph comparing the gram capacity of assembled batteries of examples 1-2, 4, 6 of the present invention and comparative examples 1 and 3.
Fig. 6 is a graph of rate performance of a cell assembled with lithium iron phosphate powder after degradation of PVDF according to example 1 of the present invention and a cell assembled with commercial powder according to comparative example 3.
Fig. 7 is a cycle performance diagram of a battery assembled by lithium iron phosphate powder after degradation of PVDF according to embodiment 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the aspects of the present invention are shown in the drawings, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Referring to fig. 1, the present invention provides a method for degrading PVDF in a positive electrode of a waste lithium iron phosphate battery, including the following steps:
s1, firstly, cleaning and coarsely crushing the waste lithium iron phosphate battery positive pole piece obtained through disassembly, then, placing the coarsely crushed positive pole piece with a preset size in a calcining device in an inert gas atmosphere, heating to 320-360 ℃ at a preset first heating rate, carrying out calcining treatment for 1-4 h, completing primary sintering, and obtaining positive pole piece powder after PVDF fails;
s2, performing air classification treatment on the positive pole piece powder with the failed PVDF obtained in the step S1 to obtain positive pole piece powder with a preset particle size;
and S3, placing the cathode powder obtained in the step S2 in a calcining device in an inert gas atmosphere, heating to 500-650 ℃ at a preset second heating rate, calcining for 0.25-4 h, completing secondary sintering, and completely carbonizing and degrading the invalid PVDF to obtain the lithium iron phosphate powder with completely degraded PVDF.
Further, in step S1, the size of the coarsely crushed pole piece is 1-10 mm.
Further, the calcining device includes but is not limited to one of a rotary kiln, a roller kiln, a tube furnace and a muffle furnace.
Further, in step S2, after the air classification treatment, the grain size of the positive powder is 5-80 μm.
Further, in step S1, the first temperature rise rate is 1 to 10 ℃/min.
Further, the inert gas is flowing gas, and the flowing speed is 0.05-10L/min.
Further, the inert gas includes, but is not limited to, one or more of nitrogen, argon, helium, and mixtures thereof.
Further, the PVDF includes but is not limited to PVDF5130 series and HSV900 series of one or more mixed.
Further, in step S3, the second temperature rise rate is 1 to 10 ℃/min.
Further, in the primary sintering process of step S1, the PVDF is cracked, and the cracked product is small-molecule organic hydrocarbons; in the secondary sintering process described in step S3, the PVDF that has failed is completely degraded and carbonized into a carbon material.
Thermogravimetric analysis of PVDF and detection of decomposition products at different temperature ranges:
referring to the Thermogravimetric (TG) analysis diagram of PVDF shown in FIG. 2, it can be seen that in the heating process of PVDF, in the temperature range of 0-320 ℃, PVDF mainly loses moisture; 320-500 ℃, PVDF mainly decomposes, and the products are low molecular chain organic hydrocarbons, methane ethylene, HF, H2 and the like; after 500 c, the PVDF was completely carbonized (shown in the table below), and the remaining carbon content ratio was close to the theoretical value of 37.5% (carbon ratio 24/64 according to the molecular structural formula of PVDF).
Test group 1:
calcining the lithium iron phosphate positive pole piece at different temperatures (300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ and 600 ℃) and different time (60min and 120min) parameter conditions to obtain a content reduction ratio curve graph of PVDF in the pole piece shown in figure 3 at different calcining temperatures, wherein the heating time is reduced to 1-2h for pursuing economic benefit, and the graph shows that the PVDF in the pole piece is calcined at different times, the reduction ratio curves are similar, which indicates that PVDF degradation reaction events at different temperatures are within 1 h; before 500 ℃, PVDF decomposes into low molecular weight products and is discharged with the gas, and after 500 ℃, the percentage of complete reduction in PVDF carbonization decreases, which is in concert with the TG curve results.
Test group 2:
the pure PVDF is calcined under different temperature (300 ℃, 380 ℃, 400 ℃, 420 ℃, 450 ℃, 550 ℃) and different time (15min, 30min, 60min, 120min, 240min) parameters to obtain the graph of the decrement ratio of the pure PVDF at different calcining temperatures as shown in fig. 4, and it can be seen that in the temperature close to 500 ℃, the decrement ratio of the PVDF after the 420 ℃ and 450 ℃ calcination is close to the theoretical ratio of complete carbonization at 500 ℃ in the TG curve, 62.5%, 100% -37.5%, and the theoretical value of 63.06% already after the 550 ℃ calcination for 15min, so the data result is corresponding to the TG result and the result in fig. 3.
According to the thermogravimetric analysis of PVDF and the detection of decomposition products at different temperature sections, the invention combines three processes of primary sintering, airflow grading and secondary sintering, and realizes the stripping of powder of the lithium iron phosphate pole piece and the complete degradation of PVDF in the lithium iron phosphate pole piece by utilizing a segmented temperature sintering process (the primary sintering temperature is 320-360 ℃ and the secondary sintering temperature is 500-650 ℃).
The present invention will be described in detail with reference to specific examples.
Example 1
S1, firstly, cleaning and coarsely crushing the waste lithium iron phosphate battery positive electrode piece obtained through disassembly, then, placing the coarsely crushed positive electrode piece with the size of about 1-10 mm in a tubular furnace in an inert gas atmosphere (nitrogen, the flow rate is 0.5L/min), heating to 360 ℃ at a first heating rate of 10 ℃/min, carrying out calcination treatment for 2 hours, completing primary sintering, cracking PVDF, wherein the cracking product is micromolecule organic hydrocarbon, and the positive electrode piece powder with failure PVDF is obtained, namely, the lithium iron phosphate powder with a relatively complete structure is stored;
s2, carrying out air flow classification treatment on the positive pole piece powder with the PVDF failed obtained in the step S1 to obtain positive pole piece powder with the particle size of 5-80 microns;
s3, placing the anode powder obtained in the step S2 after air classification in a tubular furnace in an inert gas atmosphere (argon, the flow rate is 1L/min), heating to 550 ℃ at a second heating rate of 1L/min, calcining for 1h, finishing secondary sintering, and completely carbonizing and degrading the invalid PVDF to obtain the lithium iron phosphate powder with completely degraded PVDF.
And (5) taking the PVDF completely degraded lithium iron phosphate powder obtained in the step (S3) as a positive material, and performing a battery assembly test.
Example 2
S1, firstly, cleaning and coarsely crushing the waste lithium iron phosphate battery positive electrode piece obtained through disassembly, then, placing the coarsely crushed positive electrode piece with the size of about 1-10 mm in a tubular furnace in an inert gas atmosphere (nitrogen, the flow rate is 0.1L/min), heating to 320 ℃ at a first heating rate of 5 ℃/min, calcining for 4 hours, completing primary sintering, cracking PVDF, wherein the cracking product is micromolecule organic hydrocarbon, and the positive electrode piece powder with failed PVDF is obtained, namely, the lithium iron phosphate powder with a relatively complete structure is stored;
s2, carrying out air flow classification treatment on the positive pole piece powder with the PVDF failed obtained in the step S1 to obtain positive pole piece powder with the particle size of 5-80 microns;
s3, placing the anode powder obtained after air classification in the step S2 in a tubular furnace in an inert gas atmosphere (argon, the flow rate is 10L/min), heating to 500 ℃ at a second heating rate of 10L/min, calcining for 4 hours, completing secondary sintering, and completely carbonizing and degrading the invalid PVDF to obtain the lithium iron phosphate powder with completely degraded PVDF.
And (5) taking the PVDF completely degraded lithium iron phosphate powder obtained in the step (S3) as a positive material, and performing a battery assembly test.
Example 3
S1, firstly, cleaning and coarsely crushing the waste lithium iron phosphate battery positive electrode piece obtained through disassembly, then, placing the coarsely crushed positive electrode piece with the size of about 1-10 mm in a tubular furnace in an inert gas atmosphere (helium, the flow rate is 0.9L/min), heating to 350 ℃ at a first heating rate of 2 ℃/min, carrying out calcination treatment for 2 hours, completing primary sintering, cracking PVDF, wherein the cracking product is micromolecule organic hydrocarbon, and the positive electrode piece powder with failed PVDF is obtained, namely, the lithium iron phosphate powder with a relatively complete structure is stored;
s2, carrying out air flow classification treatment on the positive pole piece powder with the PVDF failed obtained in the step S1 to obtain positive pole piece powder with the particle size of 5-80 microns;
s3, placing the airflow-graded anode powder obtained in the step S2 in a tubular furnace in an inert gas atmosphere (argon, the flow rate is 10L/min), heating to 520 ℃ at a second heating rate of 1L/min, calcining for 4 hours, completing secondary sintering, and completely carbonizing and degrading the invalid PVDF to obtain the lithium iron phosphate powder with completely degraded PVDF.
And (5) taking the PVDF completely degraded lithium iron phosphate powder obtained in the step (S3) as a positive material, and performing a battery assembly test.
Example 4
S1, firstly, cleaning and coarsely crushing the waste lithium iron phosphate battery positive electrode piece obtained through disassembly, then, placing the coarsely crushed positive electrode piece with the size of about 1-10 mm in a muffle furnace in an inert gas atmosphere (nitrogen, the flow rate is 10L/min), heating to 360 ℃ at a first heating rate of 10 ℃/min, calcining for 2 hours, completing primary sintering, cracking PVDF, wherein the cracking product is micromolecule organic hydrocarbon, and obtaining positive electrode piece powder with failed PVDF, namely, lithium iron phosphate powder with a relatively complete structure;
s2, carrying out air flow classification treatment on the positive pole piece powder with the PVDF failed obtained in the step S1 to obtain positive pole piece powder with the particle size of 5-80 microns;
s3, placing the anode powder obtained after air classification in the step S2 in a muffle furnace in an inert gas atmosphere (helium, the flow rate is 10L/min), heating to 650 ℃ at a second heating rate of 10L/min, calcining for 1h, completing secondary sintering, and completely carbonizing and degrading the invalid PVDF to obtain the lithium iron phosphate powder with completely degraded PVDF.
And (5) taking the PVDF completely degraded lithium iron phosphate powder obtained in the step (S3) as a positive material, and performing a battery assembly test.
Example 5
S1, firstly, cleaning and coarsely crushing the waste lithium iron phosphate battery positive electrode piece obtained through disassembly, then, placing the coarsely crushed positive electrode piece with the size of about 1-10 mm in a roller kiln in an inert gas atmosphere (nitrogen, the flow rate is 10L/min), heating to 355 ℃ at a first heating rate of 5 ℃/min, carrying out calcination treatment for 2 hours, completing primary sintering, cracking PVDF, wherein the cracking product is micromolecule organic hydrocarbon, and obtaining positive electrode piece powder with failed PVDF, namely, lithium iron phosphate powder with a relatively complete structure;
s2, carrying out air flow classification treatment on the positive pole piece powder with the PVDF failed obtained in the step S1 to obtain positive pole piece powder with the particle size of 5-80 microns;
s3, placing the airflow-graded anode powder obtained in the step S2 in a roller kiln in an inert gas atmosphere (nitrogen, with a flow rate of 10L/min), heating to 550 ℃ at a second heating rate of 10L/min, calcining for 2 hours, completing secondary sintering, and completely carbonizing and degrading the invalid PVDF to obtain the lithium iron phosphate powder with completely degraded PVDF.
And (5) taking the PVDF completely degraded lithium iron phosphate powder obtained in the step (S3) as a positive material, and performing a battery assembly test.
Example 6
S1, firstly, cleaning and coarsely crushing the waste lithium iron phosphate battery positive electrode piece obtained through disassembly, then, placing the coarsely crushed positive electrode piece with the size of about 1-10 mm in a rotary kiln in an inert gas atmosphere (nitrogen, the flow rate is 10L/min), heating to 350 ℃ at a first heating rate of 5 ℃/min, carrying out calcination treatment for 2 hours, completing primary sintering, cracking PVDF, wherein the cracking product is small-molecule organic hydrocarbon, and obtaining positive electrode piece powder with failed PVDF, namely, lithium iron phosphate powder with a relatively complete structure;
s2, carrying out air flow classification treatment on the positive pole piece powder with the PVDF failed obtained in the step S1 to obtain positive pole piece powder with the particle size of 5-80 microns;
s3, placing the airflow-graded anode powder obtained in the step S2 in a roller kiln in an inert gas atmosphere (nitrogen, with a flow rate of 10L/min), heating to 550 ℃ at a second heating rate of 10L/min, calcining for 2 hours, completing secondary sintering, and completely carbonizing and degrading the invalid PVDF to obtain the lithium iron phosphate powder with completely degraded PVDF.
And (5) taking the PVDF completely degraded lithium iron phosphate powder obtained in the step (S3) as a positive material, and performing a battery assembly test.
Comparative example 1
The difference from example 1 is that: the PVDF removal is carried out by adopting a wet method (NMP soaking), and comprises the following steps:
s1, the waste lithium iron phosphate battery positive pole piece obtained by disassembly is cleaned and coarsely crushed, and the coarsely crushed pole piece with the size of about 1-10 mm is soaked in NMP, wherein the mass ratio of the pole piece to the NMP is 1: 3, soaking while stirring for 18h, and then drying at 120 ℃ for 20h (wearing a mask to prevent NMP poisoning in the whole process), thereby completing stripping of the lithium iron phosphate powder and dissolution and removal of PVDF;
and S2, performing air classification on the dried lithium iron phosphate powder, controlling the particle size to obtain a positive-grade powder with the particle size, coating to manufacture a battery, and testing.
Comparative example 2
The difference from example 1 is that: the PVDF removal is carried out by a wet method (strong acid cooking), and the method comprises the following steps:
s1, firstly, cleaning and coarsely crushing the waste lithium iron phosphate battery positive electrode piece obtained through disassembly, soaking the coarsely crushed positive electrode piece with the size of about 1-10 mm in 1M hydrochloric acid solution, heating while stirring, controlling the temperature at 55 ℃, soaking for 18 hours, washing with sufficient water until the pH value is about 7-8.5, and then drying at 120 ℃ for 20 hours to complete stripping of lithium iron phosphate powder and denaturation removal of PVDF;
and S2, performing air classification on the dried lithium iron phosphate powder, controlling the particle size to obtain a positive-grade powder with the particle size, coating to manufacture a battery, and testing.
Comparative example 3
The difference from example 1 is that: and (3) carrying out battery assembly test by adopting commercial lithium iron phosphate anode powder.
The cells assembled in the above examples and comparative examples were subjected to performance tests and results analysis:
the gram capacity test method comprises the following steps: assembling and fastening the cut 14mm positive electrode wafer and the 16mm metal lithium negative electrode wafer in a glove box, standing for 12h, then loading the obtained product on a cabinet for testing, and circulating for 3 times in an environment with 2.5-4.2V, 0.1C multiplying power and 25 ℃ to obtain the average value of the discharge capacity, comparing the mass of the active substances and obtaining the gram capacity.
The test method of the multiplying power performance comprises the following steps: assembling and fastening the cut 14mm positive electrode wafer and the 16mm metal lithium negative electrode wafer in a glove box, standing for 12h, then loading the wafer on a cabinet for testing, and circulating for 5 times at 25 ℃ for 2.5-4.2V, 0.1C, 0.2C, 0.5C, 1C, 2C and 5C multiplying power to obtain multiplying power discharge data.
The test method of the cycle performance comprises the following steps: and homogenizing and coating the PVDF-degraded lithium iron phosphate pole piece to prepare a pole piece, matching a graphite negative pole to prepare a soft package, wherein the excessive coefficient of the negative pole is about 1.2, standing for 12h after liquid injection, and testing and circulating according to 2.5-3.65V and 1C multiplying power after formation.
Referring to the gram-volume comparison shown in fig. 5, it can be seen that:
the gram capacities of the batteries assembled by the lithium iron phosphate powder materials after degradation of PVDF provided in the embodiments 1 and 2 are 147mAh/g and 151mAh/g, in the embodiment 1, after one-time sintering at 360 ℃, a small amount of HF is generated by degradation of PVDF, and certain corrosion is caused to the lithium iron phosphate material, while in the embodiment 2, the one-time sintering temperature is 320 ℃, the integrity of the surface of the lithium iron phosphate material is better, and therefore the gram capacity is slightly higher.
The gram capacity of the battery assembled by the lithium iron phosphate powder provided by the comparative example 1 is 145mAh/g, and the PVDF of the lithium iron phosphate material soaked by the NMP possibly has trace residues, so that the capacity exertion is influenced.
The gram capacities of the batteries assembled by the PVDF-degraded lithium iron phosphate powder provided in examples 4 and 6 are 147mAh/g and 151mAh/g, and the difference of the gram capacities is mainly due to the corrosion of a small amount of HF on the lithium iron phosphate, so that the capacities are slightly lower.
The gram capacity of the commercial powder assembled cell provided in comparative example 3 was 149-150 mAh/g.
Therefore, the lithium iron phosphate powder with excellent electrochemical performance can be obtained by the method for degrading PVDF in the anode of the waste lithium iron phosphate battery.
Referring to the rate performance plots for example 1 (red) and comparative example 3 (black) shown in fig. 6, it can be seen that: compared with the commercial quantity, the multiplying power of lithium iron phosphate obtained by degrading PVDF by the method provided by the embodiment 1 of the invention is equivalent to 2C, and the multiplying power is slightly inferior to 5C, which is related to the growth of lithium iron phosphate crystal grains after high-temperature calcination in the embodiment 1.
Referring to the cycle performance chart of example 1 shown in fig. 7, it can be seen that the lithium iron phosphate has excellent cycle performance.
In conclusion, the invention provides a method for degrading PVDF in the anode of a waste lithium iron phosphate battery. The method adopts a three-step combined process of primary sintering, airflow classification and secondary sintering, achieves the purposes of stripping the lithium iron phosphate powder and completely degrading PVDF into a carbon material by the combination and cooperation of sintering processes at different temperature sections and airflow classification processes, effectively avoids the corrosion damage of hydrogen fluoride gas generated by the failure of PVDF on lithium iron phosphate powder particles, and also avoids the damage of the integrity of the original powder structure. The method has wide application range, is suitable for most of the existing equipment and industrial batch production, meets the requirements of energy conservation, simplicity and environmental protection, provides a new process for stripping the powder recovered from the lithium battery anode material, and has huge application prospect and economic value. .
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (10)
1. A method for degrading PVDF in the anode of a waste lithium iron phosphate battery is characterized by comprising the following steps: the method comprises the following steps:
s1, firstly, cleaning and coarsely crushing the waste lithium iron phosphate battery positive pole piece obtained through disassembly, then, placing the coarsely crushed positive pole piece with a preset size in a calcining device in an inert gas atmosphere, heating to 320-360 ℃ at a preset first heating rate, carrying out calcining treatment for 1-4 h, completing primary sintering, and obtaining positive pole piece powder after PVDF fails;
s2, performing air classification treatment on the positive pole piece powder with the failed PVDF obtained in the step S1 to obtain positive pole piece powder with a preset particle size;
and S3, placing the cathode powder obtained in the step S2 in a calcining device in an inert gas atmosphere, heating to 500-650 ℃ at a preset second heating rate, calcining for 0.25-4 h, completing secondary sintering, and completely carbonizing and degrading the invalid PVDF to obtain the lithium iron phosphate powder with completely degraded PVDF.
2. The method for degrading PVDF in the positive electrode of the waste lithium iron phosphate battery as claimed in claim 1, wherein: in step S1, the size of the coarsely crushed pole piece is 1-10 mm.
3. The method for degrading PVDF in the positive electrode of the waste lithium iron phosphate battery as claimed in claim 1, wherein: the calcining equipment comprises but is not limited to one of a rotary kiln, a roller kiln, a tube furnace and a muffle furnace.
4. The method for degrading PVDF in the positive electrode of the waste lithium iron phosphate battery as claimed in claim 1, wherein: in step S2, after the air classification treatment, the grain size of the positive powder is 5-80 μm.
5. The method for degrading PVDF in the positive electrode of the waste lithium iron phosphate battery as claimed in claim 1, wherein: in step S1, the first temperature rise rate is 1-10 ℃/min.
6. The method for degrading PVDF in the positive electrode of the waste lithium iron phosphate battery as claimed in claim 1, wherein: the inert gas is flowing gas, and the flowing speed is 0.05-10L/min.
7. The method for degrading PVDF in the positive electrode of the waste lithium iron phosphate battery as claimed in claim 1, wherein: the inert gas includes, but is not limited to, one or more of nitrogen, argon, helium.
8. The method for degrading PVDF in the positive electrode of the waste lithium iron phosphate battery as claimed in claim 1, wherein: the PVDF includes but is not limited to one or more of PVDF5130 series and HSV900 series.
9. The method for degrading PVDF in the positive electrode of the waste lithium iron phosphate battery as claimed in claim 1, wherein: in step S3, the second temperature rise rate is 1-10 ℃/min.
10. The method for degrading PVDF in the positive electrode of the waste lithium iron phosphate battery as claimed in claim 1, wherein: in the primary sintering process of step S1, the PVDF is cracked, and the cracked product is small-molecule organic hydrocarbons; in the secondary sintering process described in step S3, the PVDF that has failed is completely degraded and carbonized into a carbon material.
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| CN114249313A (en) * | 2021-12-14 | 2022-03-29 | 福州大学 | Method for recovering battery-grade iron phosphate from waste lithium iron phosphate powder |
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