CN116247321A - Method for recycling waste lithium ion batteries through full components - Google Patents
Method for recycling waste lithium ion batteries through full components Download PDFInfo
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- CN116247321A CN116247321A CN202310037481.2A CN202310037481A CN116247321A CN 116247321 A CN116247321 A CN 116247321A CN 202310037481 A CN202310037481 A CN 202310037481A CN 116247321 A CN116247321 A CN 116247321A
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- graphite powder
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 57
- 239000002699 waste material Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000004064 recycling Methods 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000003792 electrolyte Substances 0.000 claims abstract description 48
- 239000000843 powder Substances 0.000 claims abstract description 28
- 208000028659 discharge Diseases 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 24
- 238000012216 screening Methods 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011162 core material Substances 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 15
- 239000007900 aqueous suspension Substances 0.000 claims description 13
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 11
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 11
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 22
- 230000000052 comparative effect Effects 0.000 description 11
- 239000010439 graphite Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 101150058243 Lipf gene Proteins 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 229910013872 LiPF Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/215—Purification; Recovery or purification of graphite formed in iron making, e.g. kish graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/0038—Obtaining aluminium by other processes
- C22B21/0069—Obtaining aluminium by other processes from scrap, skimmings or any secondary source aluminium, e.g. recovery of alloy constituents
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- 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 belongs to the technical field of waste lithium ion battery recovery, and particularly relates to a method for full-component recovery of waste lithium ion batteries. The invention provides a method for recycling waste lithium ion batteries by full components, which is characterized in that the full components of battery shells, electrolyte, diaphragms, copper powder, aluminum powder, graphite powder and anode powder of the waste lithium ion batteries are recycled by combining discharge treatment, crushing treatment, electrolyte recycling, sorting and screening, the whole separation process is efficient and rapid, wherein the electrolyte recycling rate is above 95.21%, the diaphragm material recycling rate is above 99.18%, the copper powder and aluminum powder purity is above 97.32%, and the purity of graphite powder and anode powder is above 97.61%.
Description
Technical Field
The invention belongs to the technical field of waste lithium ion battery recovery, and particularly relates to a method for full-component recovery of waste lithium ion batteries.
Background
The lithium ion battery in China always keeps a strong growth situation in recent years, the service life of the lithium ion battery is usually 3-5 years, and the lithium battery scrapped after reaching the service life is also growing at a bursting speed year by year. The lithium ion battery consists of a positive electrode material, a negative electrode material, an organic diaphragm, electrolyte and a shell. The positive electrode material mainly comprises aluminum foil and active substances bonded on the surface of the aluminum foil, such as lithium cobaltate, lithium nickel cobalt manganate, lithium iron phosphate and the like; the negative electrode material mainly comprises a copper foil and graphite powder bonded on the surface of the copper foil; the electrolyte mainly contains carbonate organic solvent and lithium hexafluorophosphate; the diaphragm is a polymer film, which can let lithium ions pass freely, but electrons cannot.
The waste lithium ion battery contains 5-20% of cobalt, 5-10% of nickel, 5-7% of lithium, 15% of organic compound, 7% of plastic and the like. If the scrapped lithium ion battery is not treated, the scrapped lithium ion battery is piled up to easily generate the risk of ignition or explosion, meanwhile, electrolyte in the lithium ion battery contains organic matters such as Ethylene Carbonate (EC), diethyl carbonate (DEC), dimethyl sulfate (DMC) and the like, and LiPF in the electrolyte 6 The hydrogen fluoride gas is easy to react with water to generate hydrogen fluoride gas, and the hydrogen fluoride gas is toxic and has high corrosiveness and can generate serious water and environmental pollution. Therefore, the method has profound significance for effectively recycling the lithium ion battery, recycling rare metals, reducing environmental pollution and promoting the sustainable development of new energy industry.
Chinese patent CN 114361636A discloses a method for cleaning and recycling waste lithium ion batteries, which comprises the steps of fully discharging the waste lithium ion batteries in a metal salt solution, and then crushing and carbonizing the fully discharged waste lithium ion batteriesRoasting, namely discharging gas generated in the carbonization roasting process after reaching standards through treatment and detection, further crushing the carbonized sheet material, carrying out air separation after crushing to separate a diaphragm, screening the powder remained after air separation to obtain copper-aluminum mixed powder and battery black powder, finally separating the copper-aluminum mixed powder through color separation to obtain copper powder and aluminum powder, and carrying out flotation on the battery black powder to obtain anode powder and graphite powder. However, in pretreatment, the waste lithium ion battery is directly put into a metal salt solution for discharging, so that the problem that the discharging time rate is slow and the production efficiency is affected exists; meanwhile, the waste lithium ion batteries are crushed and then are directly carbonized and roasted, the electrolyte is not effectively recycled, the electrolyte accounts for about 8% of the batteries, and the LiPF in the electrolyte is caused 6 Raw material prices rise year by year, so that the recovery process of the waste lithium ion batteries needs to be optimized.
Disclosure of Invention
Aiming at the problems, the invention provides a method for recycling the waste lithium ion battery by using all components, which can realize the efficient recycling of all components in the waste lithium ion battery, and the method improves the discharge rate of the waste lithium ion battery and accelerates the production efficiency by utilizing the conductivity and chemical inertness of graphite and combining ultrasonic treatment during pretreatment; and meanwhile, the crushed battery core is dissolved in an organic solvent and is combined with microwave treatment, so that the electrolyte in the waste lithium ion battery is effectively recovered. And full-component recovery is carried out on the diaphragm, copper powder, aluminum powder, graphite powder and positive electrode powder in the waste lithium ion battery by adopting an air flow separation and color separation combined screening physical separation technology.
In order to solve the technical problems of the invention, the invention adopts the following technical scheme:
the invention aims to provide a method for recycling waste lithium ion batteries by using all components, which comprises the following steps:
s1, discharge treatment: placing the waste lithium ion battery into a water suspension containing graphite powder, performing ultrasonic auxiliary discharge treatment for 4-6h, and filtering;
s2, crushing: firstly, primarily disassembling filter residues obtained by filtering the S1, separating to obtain a battery shell and a battery core, and performing primary crushing treatment in a protective gas atmosphere after the battery core is subjected to low-temperature freeze-drying treatment;
s3, recycling electrolyte: dissolving the battery core material after the S2 crushing treatment in an organic solvent, carrying out microwave treatment for 1-2h, and filtering to obtain filtrate, namely a recovered electrolyte; when the recycled electrolyte is used in the later period, the content of conductive lithium salt in the electrolyte can be measured, and the electrolyte is prepared to a proper concentration to be used as the electrolyte of a lithium battery for recycling.
S4, sorting: performing secondary crushing treatment on filter residues obtained by filtering in the step S3, and separating out a diaphragm by using an airflow separator; then adopting color separation to obtain copper powder, aluminum powder and a mixed material 1 containing graphite powder and positive electrode powder respectively;
the air flow separator takes air as a separation medium, particles are separated according to density or granularity under the action of air flow, lighter materials are taken upwards or are taken to a far place from the horizontal direction by the air flow, and heavy materials are settled because the upward air flow cannot support the heavy materials or can not be greatly changed in direction because of enough inertia of the heavy materials to pass through the air flow for settlement. The battery diaphragm generally adopts a polyolefin porous film with high strength and thinned, the density is low, the diaphragm can be effectively separated by using the method, and the recovery rate of the diaphragm material is more than 99.18 percent.
The battery materials mainly comprise dark red copper powder, silver gray and silver bright aluminum powder, black graphite powder and positive electrode powder, and according to the difference of colors, the copper powder and the aluminum powder can be separated by a color selection process, and the purity of the separated copper powder and aluminum powder is above 97.32%.
S5, screening: and (3) separating the mixed material 1 obtained in the step (S4) in a frequency modulation vibration screening mode to obtain graphite powder and positive electrode powder respectively.
The graphite powder and the positive electrode powder are different in granularity and specific gravity and separated in a frequency modulation vibration screening mode to obtain the graphite powder and the positive electrode powder respectively, and the purity of the recovered graphite powder and the recovered positive electrode powder is higher than 97.61%.
Further, in S1, in the aqueous suspension containing graphite powder, the mass ratio of the graphite powder to the water is 0.2-0.3:1;
the mass ratio of the waste lithium ion battery to the graphite powder-containing water suspension is 1-2:1.
The graphite has excellent conductivity and chemical inertness, and the graphite is used as a conductive medium, so that the traditional salt solution or alkali solution can avoid the dissolution loss of the waste lithium ion battery shell and the pollution of an electrolyte system by corroding electrodes. Meanwhile, because graphite has chemical inertness, chemical reaction is not easy to generate toxic and harmful gases, so that environmental pollution is caused.
Further, in S1, the frequency of the ultrasonic wave is 10-20kHz. The mechanical vibration and cavitation of the ultrasonic wave can accelerate the vibration and diffusion of molecules, so that the water suspension system of the graphite powder is more uniform, the movement and fluidity of the graphite powder are accelerated, and the discharge rate of the waste lithium ion battery is improved.
Further, in S2, the low-temperature freeze-drying temperature is-30 to-20 ℃; the freeze-drying is carried out in a low-temperature environment, so that the brittleness of the battery core can be increased, the subsequent crushing treatment of the battery core is facilitated, and the separation of the positive electrode plate and the negative electrode plate from the electrode powder is facilitated.
The protective atmosphere is one of nitrogen and argon; liPF in electrolyte 6 Poor thermal stability, easy reaction with water to produce hydrogen fluoride gas, which is toxic and highly corrosive to avoid LiPF 6 The electrolyte is released after the battery cells are crushed by reacting with steam in the air, so that the battery cells are crushed in a protective gas atmosphere.
The crushing granularity of the primary crushing is 1-2cm.
Further, in S3, the organic solvent is one or more of ethylene carbonate, diethyl carbonate, and dimethyl sulfate. LiPF in electrolyte 6 Is easily dissolved in aprotic organic solvents such as low-concentration carbonic ester, etc., and ethylene carbonate, diethyl carbonate and dimethyl sulfate are all common organic matters in battery electrolyte, and one or more of ethylene carbonate, diethyl carbonate and dimethyl sulfate are specially selected asTo recover the organic solvent of the electrolyte.
Further, in S3, the microwave power is 250-300W. The microwaves have excellent penetrability, which is helpful for the electrolyte to quickly escape from the battery core, and fully dissolve in the organic solvent, thereby improving the recovery rate of the electrolyte.
Further, in S4, the mixture is crushed again until the granularity is smaller than 5mm.
Further, in S5, the mesh number of the frequency modulation vibration screening is 200-300 mesh, the screening frequency is 20-50Hz, and the inclination angle of the screen is 10-30 degrees. The frequency modulation vibrating screen can effectively avoid the problems of easy agglomeration and easy adsorption of graphite powder and positive electrode powder, and realize good separation effect of the graphite powder and the positive electrode powder.
Further, the graphite powder recovered in S5 may be used as a raw material of the graphite powder in S1.
Further, steps S2-S5 are all performed in a closed environment.
The invention has the beneficial effects that:
1. the traditional hydrometallurgy method for recycling the waste lithium ion batteries needs to use a large amount of strong acid and strong alkali substances, and when the treatment is improper, the environment pollution can be caused; the traditional pyrometallurgical method has higher energy consumption and generates a large amount of waste gas. The invention provides a method for recycling waste lithium ion batteries by full components, which realizes the full component recycling of battery shells, electrolyte, diaphragms, copper powder, aluminum powder, graphite powder and positive electrode powder of the waste lithium ion batteries by combining discharge treatment, crushing treatment, electrolyte recycling, sorting and screening, and the whole separation process is efficient and rapid.
2. Before the waste lithium ion battery materials are separated, the electric conductivity and chemical inertness of graphite are utilized, and the mechanical vibration and cavitation of ultrasonic waves are combined to accelerate the vibration and diffusion of molecules, so that a water suspension system of graphite powder is more uniform, the movement and fluidity of the graphite powder are accelerated, the discharge rate of the waste lithium ion battery is improved, and the production efficiency is accelerated.
3. LiPF in electrolyte 6 Is easy to be dissolved in aprotic organic solvents such as low-concentration carbonic esters, and the like, and ethylene carbonate, diethyl carbonate and dimethyl sulfate are all battery electricityOrganic matters commonly used in the electrolyte are selected from one or more of ethylene carbonate, diethyl carbonate and dimethyl sulfate as organic solvents for recovering the electrolyte. When the electrolyte is recovered, the microwave auxiliary treatment is combined, so that the electrolyte can quickly escape from the battery core and is fully dissolved in the organic solvent, and the recovery rate of the electrolyte is improved.
4. In the purification process, an air flow separation and color separation combined screening physical separation technology is creatively adopted, the color, granularity and specific gravity difference of crushed materials are utilized to recover the whole components of the waste lithium ion battery, wherein the recovery rate of electrolyte is more than 95.21%, the recovery rate of diaphragm materials is more than 99.18%, the purities of copper powder and aluminum powder are more than 97.32%, and the purities of graphite powder and positive electrode powder are more than 97.61%, so that the method is simple and feasible, low in operation difficulty, environment-friendly, low in investment cost and good in popularization and application value.
Detailed Description
For the purposes of and some of the embodiments of the present invention, the following description will clearly and fully describe the embodiments of the present invention in conjunction with the detailed description, and it is evident that the described embodiments are only some, but not all, examples of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1: full-component recovery waste lithium ion battery
S1, discharge treatment: placing the waste lithium ion battery into a water suspension containing graphite powder (the mass ratio of the graphite powder to water is 0.2:1), performing ultrasonic auxiliary discharge treatment, treating for 4 hours at an ultrasonic frequency of 20kHz, and filtering;
s2, crushing: firstly, primarily disassembling filter residues obtained by filtering the S1, separating to obtain a battery shell and a battery core, performing freeze drying treatment at a low temperature of-20 ℃ on the battery core, and performing primary crushing treatment in a nitrogen atmosphere, wherein the crushing granularity is 1-2cm;
s3, recycling electrolyte: dissolving the battery core material after the S2 crushing treatment in an organic solvent (the volume ratio of ethylene carbonate to diethyl carbonate to dimethyl sulfate is 1:1:1), carrying out microwave treatment for 2 hours, wherein the microwave power is 280W, and filtering to obtain filtrate, namely a recovered electrolyte;
s4, sorting: performing secondary crushing treatment on filter residues obtained by filtering in the step S3 until the granularity is less than 5mm, and separating a diaphragm by using an airflow separator; then adopting color separation to obtain copper powder, aluminum powder and a mixed material 1 containing graphite powder and positive electrode powder respectively;
s5, screening: and (3) separating the mixed material 1 obtained in the step (S4) by a frequency modulation vibration screening mode, wherein the inclination angle of the screen is 20 degrees, and screening the mixed material with a 200-mesh screen at a screening frequency of 50Hz to obtain graphite powder and positive electrode powder respectively.
Example 2: full-component recovery waste lithium ion battery
S1, discharge treatment: placing the waste lithium ion battery into a water suspension containing graphite powder (the mass ratio of the graphite powder to water is 0.3:1), performing ultrasonic auxiliary discharge treatment, wherein the ultrasonic frequency is 15kHz, treating for 5 hours, and filtering;
s2, crushing: firstly, primarily disassembling filter residues obtained by filtering the S1, separating to obtain a battery shell and a battery core, performing low-temperature freeze drying treatment at the temperature of minus 30 ℃ on the battery core, and performing primary crushing treatment in nitrogen atmosphere, wherein the crushing granularity is 1-2cm;
s3, recycling electrolyte: dissolving the battery core material after the S2 crushing treatment in an organic solvent (the volume ratio of ethylene carbonate to diethyl carbonate to dimethyl sulfate is 1:1:1), carrying out microwave treatment for 1.5 hours, wherein the microwave power is 250W, and filtering to obtain filtrate, namely a recovered electrolyte;
s4, sorting: performing secondary crushing treatment on filter residues obtained by filtering in the step S3 until the granularity is less than 5mm, and separating a diaphragm by using an airflow separator; then adopting color separation to obtain copper powder, aluminum powder and a mixed material 1 containing graphite powder and positive electrode powder respectively;
s5, screening: and (3) separating the mixed material 1 obtained in the step (S4) by a frequency modulation vibration screening mode, wherein the inclination angle of the screen is 30 degrees, and screening the mixed material with a 200-mesh screen at a screening frequency of 40Hz to obtain graphite powder and positive electrode powder respectively.
Example 3: full-component recovery waste lithium ion battery
S1, discharge treatment: placing the waste lithium ion battery into a water suspension containing graphite powder (the mass ratio of the graphite powder to water is 0.25:1), performing ultrasonic auxiliary discharge treatment, wherein the ultrasonic frequency is 10kHz, treating for 6 hours, and filtering;
s2, crushing: firstly, primarily disassembling filter residues obtained by filtering the S1, separating to obtain a battery shell and a battery core, performing freeze drying treatment at a low temperature of-25 ℃ on the battery core, and performing primary crushing treatment in a nitrogen atmosphere, wherein the crushing granularity is 1-2cm;
s3, recycling electrolyte: dissolving the battery core material after the S2 crushing treatment in an organic solvent (the volume ratio of ethylene carbonate to diethyl carbonate to dimethyl sulfate is 1:1:1), carrying out microwave treatment for 1h, wherein the microwave power is 300W, and filtering to obtain filtrate, namely a recovered electrolyte;
s4, sorting: performing secondary crushing treatment on filter residues obtained by filtering in the step S3 until the granularity is less than 5mm, and separating a diaphragm by using an airflow separator; then adopting color separation to obtain copper powder, aluminum powder and a mixed material 1 containing graphite powder and positive electrode powder respectively;
s5, screening: and (3) separating the mixed material 1 obtained in the step (S4) by a frequency modulation vibration screening mode, wherein the inclination angle of the screen is 10 degrees, and screening the mixed material with a 200-mesh screen at a screening frequency of 30Hz to obtain graphite powder and positive electrode powder respectively.
Comparative example 1:
the electrolyte was recovered without performing microwave-assisted treatment, otherwise, the same as in example 1.
The recovery rates of the components recovered in examples 1 to 3 were counted, the results are shown in Table 1, and the purity of the recovered components was measured, and the results are shown in Table 2.
TABLE 1 recovery rate Table for each component of waste lithium ion battery
TABLE 2 purity of components of waste lithium ion batteries
From the results shown in tables 1 and 2, the recovery rate of the full component recovery method of the waste lithium ion battery in the embodiment 1-3 of the invention to the electrolyte, the diaphragm, the copper powder, the aluminum powder, the positive electrode powder and the graphite powder in the waste lithium ion battery is above 95.21%, and the purity of the separated copper powder, aluminum powder, positive electrode powder and graphite powder is above 97.32%, which indicates that the full component recovery method of the waste lithium ion battery can realize the efficient recovery of the full component of the waste lithium ion battery. In comparative example 1, the recovery rate of the electrolyte was 89.68%, and it was demonstrated that the recovery rate of the electrolyte was improved by performing the microwave-assisted treatment when the electrolyte was recovered.
And under different conditions, the discharge efficiency of the waste lithium ion battery is examined.
Comparative example 2: the ultrasonic auxiliary treatment was not performed, and other discharge treatment conditions were the same as in example 1.
Comparative example 3: the aqueous suspension containing graphite powder was not added, and 8% NaCl solution was used, and the other discharge treatment conditions were the same as in example 1.
Comparative example 4: the mass ratio of graphite powder to water was 0.1:1, and other discharge treatment conditions were the same as in example 1.
Comparative example 5: the mass ratio of graphite powder to water was 1:1, and other discharge treatment conditions were the same as in example 1.
The discharge voltage changes for example 1 and comparative examples 2-5 are shown in Table 3.
Table 3 voltage change table
From Table 3, it can be seen that, in example 1, the water suspension treatment of ultrasonic wave and graphite powder is adopted, graphite can fully contact with the waste lithium ion battery, the discharge effect is good, the discharge speed is high, and the complete discharge can be realized for 4 hours. In comparative example 2, no ultrasonic auxiliary treatment is performed, the discharge rate of the waste lithium ion battery is slower, 2.46V voltage is still remained at 72h, in comparative example 3, 8% NaCl solution is adopted to match with ultrasonic treatment, and complete discharge can be realized at 6h, but the electrode is corroded, and electrolyte leaks. In comparative example 4, the discharge rate was slow when the amount of graphite powder used as a conductive medium was small, and a voltage of 1.14V remained at 72 hours, and in comparative example 5, when the amount of conductive medium was large, a voltage of 0.75V remained at 72 hours, which was related to the large amount of graphite powder used, and thus the discharge efficiency was affected.
While the preferred embodiments of the present patent have been described in detail, the present patent is not limited to the above embodiments, and other various modifications and variations may be made within the knowledge of those skilled in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. The method for recycling the waste lithium ion battery by using the whole components is characterized by comprising the following steps:
s1, discharge treatment: placing the waste lithium ion battery into a water suspension containing graphite powder, performing ultrasonic auxiliary discharge treatment for 4-6h, and filtering;
s2, crushing: firstly, primarily disassembling filter residues obtained by filtering the S1, separating to obtain a battery shell and a battery core, and performing primary crushing treatment in a protective gas atmosphere after the battery core is subjected to low-temperature freeze-drying treatment;
s3, recycling electrolyte: dissolving the battery core material after the S2 crushing treatment in an organic solvent, carrying out microwave treatment for 1-2h, and filtering to obtain filtrate, namely a recovered electrolyte;
s4, sorting: performing secondary crushing treatment on filter residues obtained by filtering in the step S3, and separating out a diaphragm by using an airflow separator; then adopting color separation to obtain copper powder, aluminum powder and a mixed material 1 containing graphite powder and positive electrode powder respectively;
s5, screening: and (3) separating the mixed material 1 obtained in the step (S4) in a frequency modulation vibration screening mode to obtain graphite powder and positive electrode powder respectively.
2. The method according to claim 1, wherein in S1, the mass ratio of graphite powder to water in the aqueous suspension containing graphite powder is 0.2-0.3:1;
the mass ratio of the waste lithium ion battery to the graphite powder-containing water suspension is 1-2:1.
3. The method according to claim 1, wherein in S1, the ultrasonic wave has a frequency of 10-20kHz.
4. The method according to claim 1, wherein in S2, the low temperature freeze-drying temperature is-30 to-20 ℃;
the protective atmosphere is one of nitrogen and argon;
the crushing granularity of the primary crushing is 1-2cm.
5. The method according to claim 1, wherein in S3, the organic solvent is one or more of ethylene carbonate, diethyl carbonate, and dimethyl sulfate.
6. The method of claim 1, wherein in S3, the microwave power is 250-300W.
7. The method of claim 1, wherein in S4, the secondary crushing is performed to a particle size of less than 5mm.
8. The method according to claim 1, wherein in S5, the mesh number of the frequency modulated vibration sieve is 200-300 mesh, the sieving frequency is 20-50Hz, and the sieve inclination angle is 10-30 °.
9. The method according to claim 1, wherein the graphite powder recovered in S5 is used as a raw material for the graphite powder in S1.
10. The method according to claim 1, wherein steps S2-S5 are all performed in a closed environment.
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| CN116826226A (en) * | 2023-06-28 | 2023-09-29 | 科立鑫(珠海)新能源有限公司 | Lithium ion battery recycling method |
| CN116826226B (en) * | 2023-06-28 | 2024-01-23 | 科立鑫(珠海)新能源有限公司 | Lithium ion battery recycling method |
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