CN114171813B - Method for magnetic separation of anode and cathode powder from waste lithium batteries - Google Patents
Method for magnetic separation of anode and cathode powder from waste lithium batteries Download PDFInfo
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- CN114171813B CN114171813B CN202111165330.2A CN202111165330A CN114171813B CN 114171813 B CN114171813 B CN 114171813B CN 202111165330 A CN202111165330 A CN 202111165330A CN 114171813 B CN114171813 B CN 114171813B
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- 239000000843 powder Substances 0.000 title claims abstract description 109
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 55
- 239000002699 waste material Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000007885 magnetic separation Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- 239000003792 electrolyte Substances 0.000 claims abstract description 22
- 239000000696 magnetic material Substances 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010405 anode material Substances 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 239000011888 foil Substances 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 15
- 238000006722 reduction reaction Methods 0.000 claims abstract description 14
- 239000011889 copper foil Substances 0.000 claims abstract description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000005389 magnetism Effects 0.000 claims abstract description 9
- 239000007774 positive electrode material Substances 0.000 claims abstract description 9
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 8
- 239000000853 adhesive Substances 0.000 claims abstract description 6
- 230000001070 adhesive effect Effects 0.000 claims abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 239000010439 graphite Substances 0.000 claims abstract description 6
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 5
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 5
- 238000010008 shearing Methods 0.000 claims abstract description 3
- 238000000197 pyrolysis Methods 0.000 claims description 32
- 239000006148 magnetic separator Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000002485 combustion reaction Methods 0.000 claims description 8
- 230000006698 induction Effects 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002912 waste gas Substances 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 34
- 229910052751 metal Inorganic materials 0.000 abstract description 20
- 239000002184 metal Substances 0.000 abstract description 20
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 239000010949 copper Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 238000000926 separation method Methods 0.000 description 13
- 150000002739 metals Chemical class 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 239000010406 cathode material Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- WPPDFTBPZNZZRP-UHFFFAOYSA-N aluminum copper Chemical compound [Al].[Cu] WPPDFTBPZNZZRP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006246 high-intensity magnetic separator Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B7/00—Combinations of wet processes or apparatus with other processes or apparatus, e.g. for dressing ores or garbage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
- B03B9/06—General arrangement of separating plant, e.g. flow sheets specially adapted for refuse
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
- B03B9/06—General arrangement of separating plant, e.g. flow sheets specially adapted for refuse
- B03B2009/066—General arrangement of separating plant, e.g. flow sheets specially adapted for refuse the refuse being batteries
-
- 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
- Y02W30/52—Mechanical processing of waste for the recovery of materials, e.g. crushing, shredding, separation or disassembly
-
- 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 discloses a method for separating anode and cathode powder from waste lithium batteries by magnetic separation. Adopting a shearing crusher to crush the waste lithium batteries in a charged state at one time under the nitrogen atmosphere, wherein crushed materials are in a large sheet shape of 30-40 mm; carbon dioxide gas generated by high-temperature decomposition of electrolyte, graphite in crushed materials, carbon generated by decomposition of a diaphragm and an adhesive in an anode and a cathode are taken as a carbon reducing agent together to generate a carbon reduction reaction with the anode material of the waste lithium battery, so that magnetism is given to the anode material. And separating the magnetic positive electrode material from the non-magnetic material by adopting a strong magnetic separation system, and separating by a hydrodynamic force separator to finally obtain positive electrode powder, negative electrode powder, aluminum foil and copper foil. The recovery rate of the anode powder, the cathode powder and the metal is above 98%, and the grade is high; the recovery process simultaneously recovers the metal aluminum and copper, and the recovery utilization yield is improved by 25%; the invention can treat ternary lithium batteries and lithium iron phosphate batteries, is suitable for large-scale industrial production, and has extremely high economic benefit.
Description
Technical Field
The invention relates to recycling of lithium batteries, in particular to a method for separating anode and cathode powders from waste lithium batteries by magnetic separation.
Background
Since 2014, new energy automobiles in China are popularized in a large quantity, the sales volume is first in the world, the annual sales volume of the new energy automobiles rises year by year, and the latest data show that the new energy automobiles in China keep about 603 thousands of new energy automobiles in quantity, and account for about 50% of the total new energy automobiles in the world. According to the service life of the lithium power battery of the new energy vehicle of 5-8 years, china is faced with a large amount of scrapped and recovered lithium power batteries in year 2020.
The data of the China automobile technical research center shows that the accumulated retirement amount of the power battery in 2020 is about 20 ten thousand tons, and the accumulated retirement amount in 2025 is estimated to be about 78 ten thousand tons. The economic benefit of recovering the valuable metals such as lithium, cobalt, nickel, manganese and the like contained in the old lithium battery is quite remarkable.
Raw materials such as cobalt, nickel, lithium and the like required by the power battery are very important strategic resources, but China cannot meet domestic demands in the aspect of mineral reserves of nonferrous metals such as cobalt, lithium, nickel and the like, 80% of cobalt and 70% of lithium and nickel resources are imported at present, and obviously recycling valuable metals from old lithium batteries is an important way for solving the domestic demands.
At present, most of the old lithium batteries are recycled by adopting a traditional method, after a PACK bag is disassembled, crushing, pyrolysis and separation are carried out, and finally, the mixed black powder of positive and negative electrodes is used as a product. For example, the invention 201811288947.1 relates to a crushing and sorting process of waste lithium ion batteries, and only positive and negative mixed powder is obtained finally. The invention 201810711557.4 relates to a physical recovery process of a lithium battery, and the final product is also positive and negative electrode mixed powder.
However, the recovery of valuable components by using anode-cathode mixed black powder as a hydrometallurgical raw material is extremely unreasonable in both process rationality and carbon emission reduction. In the subsequent hydrometallurgical process, the negative electrode graphite powder does not contain nickel, cobalt and manganese, only contains lithium elements, and is leached only by water on the premise of being subjected to reduction roasting, so that a lithium ion-containing solution is obtained, and the nickel, cobalt and manganese of the positive electrode material are leached by strong acid and a reducing agent, so that a nickel, cobalt and manganese ion-containing solution is obtained. The negative electrode powder and the positive electrode powder contain different valuable components and different treatment processes are adopted. And the negative graphite powder and the positive powder are mixed together for treatment, and the following unreasonable exists: on one hand, the negative electrode powder occupies half of the volume of the black powder, so that the processing capacity of leaching equipment is reduced, and the lithium element contained in the negative electrode is lost in the extraction and separation processes of valuable metals, so that the recovery rate of lithium is lower; thirdly, the graphite powder can only be discharged as insoluble slag, valuable elements and leached acid in the anode can be entrained, the leached material is consumed more, the recovery cost is increased, the recovery rate of the valuable elements is reduced, and finally, the graphite powder slag has the risk of being determined as dangerous chemicals due to the entrainment of metal and acid. The above aspects show that the recycling process only produces the mixed black powder of the anode and the cathode.
Currently, wet recycling enterprises of old lithium batteries are more inclined to process separated positive and negative electrode powders.
Positive and negative electrode powders are respectively obtained from the recovery process of waste lithium batteries, and two methods of gravity separation and magnetic separation are mainly adopted. The invention 201910045259.0 relates to a waste lithium battery recycling process, wherein after the waste lithium battery is crushed, iron is separated from primary crushed materials through magnetic separation, after the primary crushed materials are deeply crushed, positive electrode materials and negative electrode materials are obtained through a gravity separator, and then the positive electrode materials are separated through air flow to obtain aluminum powder and positive electrode powder. The invention has the defects that the dry gravity separation can not completely separate the anode material and the cathode material, the anode material and the cathode material after deep crushing can be mixed with each other, and the recovery rate and the grade of the anode powder and the cathode powder can not be very high; secondly, the treatment process is not environment-friendly, overflowed electrolyte is only absorbed and recovered by an electrolyte absorbing device during crushing, and the whole process is polluted by the electrolyte; dry winnowing cannot completely avoid dust overflow, dust in the field is much, and workshop dust is at explosion risk.
The invention 20191082119. X relates to a method for recycling valuable metals nickel cobalt manganese in waste lithium batteries in a green and efficient way, wherein the lithium batteries are subjected to self-discharge and then crushing, pyrolysis is carried out at a high temperature of 400-450 ℃, materials are screened by a high-frequency vibrating screen, positive electrode materials are separated, wet-grinding is carried out on the positive electrode materials, a hydrocyclone is used for grading, ore pulp overflowed by the hydrocyclone is subjected to magnetic separation by a high-gradient high-intensity magnetic separator. The essence of the invention is that the vibrating screen is adopted to screen and separate the anode material, the anode powder and the cathode powder are more mixed with each other, the grade is not high, the anode material is subjected to wet grinding, classification and magnetic separation in the follow-up process, the anode powder is subjected to repeated loss, and the recovery rate of the anode powder is low. Secondly, the pyrolysis temperature is low, the PVDF as an adhesive in the anode cannot be completely decomposed, and fluorine components can enter materials in each subsequent process; the salt solution soaking method is adopted for pre-discharging, and the electrolyte permeated into the salt solution pollutes the environment in the subsequent treatment process. The recovery method can only recover part of the positive electrode powder, other metals are difficult to recover, and the economic benefit can not meet the value-added requirements of enterprises.
The invention 201911301731.9 relates to a method and a device for separating anode and cathode materials of waste lithium batteries, which are characterized in that the anode and cathode materials of the waste lithium batteries are reduced and roasted at a high temperature of 850-1000 ℃ for 2-5 hours, co and Ni metals in the anode materials are converted into magnetic simple substance metal forms, and then the simple substance metal forms are ground to prepare 8-20% slurry, and the anode materials and graphite are obtained through two-stage magnetic separation. The invention needs high-temperature roasting to reduce metal, and has longer reduction time and high energy consumption; the roasting temperature is higher than the melting point of the aluminum foil, and the aluminum foil is fused and adhered with the anode and cathode materials, so that the magnetic separation efficiency is affected. The materials are ground to prepare slurry, copper powder, aluminum powder and non-magnetic negative electrode powder are mixed, the negative electrode powder needs to be further separated and purified, the recovery rate and grade are difficult to ensure, and the economic benefit of the recovery process is not obvious.
Therefore, it is necessary to provide a method which is economical and suitable for large-scale production, has high recovery rate, saves energy and reduces emission in the recovery process, is environment-friendly, has no secondary pollution, can recover valuable metals at the same time, and can effectively separate the positive electrode powder from the negative electrode powder.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for separating positive and negative electrode powder from waste lithium batteries by magnetic separation, wherein the magnetic separation is realized by endowing the broken positive electrode plates of the waste lithium batteries with magnetism through high-temperature pyrolysis and carbon reduction, so that the problems that the positive electrode and the negative electrode cannot be effectively separated, the recovery rate is low, the grade of the positive electrode powder and valuable metal is low, the energy conservation and emission reduction are not met, the dust in site environment is much, and potential safety hazards exist in the prior art are solved.
The invention is realized by adopting the following technical scheme:
a method for magnetically separating anode and cathode powder from waste lithium batteries comprises the following steps:
(1) Under the protection of nitrogen, a shearing crusher is adopted to crush the waste lithium batteries once, volatilized electrolyte is sent into a pyrolysis gas combustion treatment system for treatment, and the purified electrolyte reaches the discharge standard;
(2) In nitrogen atmosphere, pyrolyzing the crushed material obtained in the step (1) at 500-600 ℃, carrying out high-temperature decomposition on the electrolyte to generate carbon dioxide gas, decomposing graphite in the crushed material, and decomposing carbon generated by the bonding agent in the diaphragm and the anode and the cathode to jointly serve as a carbon reducing agent, carrying out carbon reduction reaction with the anode material of the waste lithium battery, endowing the anode material with magnetism (transition metal in the anode material is reduced and converted into low-valence oxide with magnetism), and introducing the burnt waste gas into a pyrolysis gas combustion treatment system for treatment, and purifying and then discharging the waste gas reaching standards;
the carbon reduction reaction is shown in the following reaction formula:
LiNi x Co y Mn z O 2 +CO→Li 2 CO 3 +NiO+CoO+MnO+CO 2 +O 2 (a)
C+CO 2 ＝2CO (b)
(3) Separating magnetic materials and non-magnetic materials by a strong magnetic separation system, wherein the magnetic materials comprise positive electrode plates, positive electrode powder (a small amount of positive electrode mixed materials), a magnetic shell and a pile head, and the non-magnetic materials comprise negative electrode plates, negative electrode powder negative electrode mixed materials, a non-magnetic shell and a pile head;
(4) Separating the heavy magnetic shell and pile head from the magnetic materials by a hydrodynamic force separator, namely separating the light positive electrode mixed materials comprising a positive electrode plate and positive electrode powder, then stripping the positive electrode powder on the positive electrode plate by a wet stripping system, sieving, separating wet positive electrode powder and aluminum foil, dehydrating and drying the positive electrode powder to obtain product positive electrode powder, and drying the wet aluminum foil to obtain aluminum foil byproducts;
(5) Separating the non-magnetic materials into heavy shells and pile heads by a hydrodynamic force separator, namely, light negative electrode mixed materials comprising a negative electrode plate and negative electrode powder, stripping the upper electrode powder of the negative electrode plate by a wet stripping system, and sieving and separating wet negative electrode powder and copper foil; and (5) dehydrating and drying the negative electrode powder to obtain the product negative electrode powder, and drying the wet copper foil to obtain a copper foil byproduct.
Further, the waste lithium battery is a ternary battery or a lithium iron phosphate battery.
Further, in the step (1), the crushed materials of the waste lithium batteries are in a large piece shape of 30-40 mm.
Further, the high-temperature pyrolysis temperature is preferably 530-570 ℃; under the temperature and under the nitrogen atmosphere, carbon dioxide gas generated by the decomposition of electrolyte in the waste lithium battery, carbon generated by the decomposition of a diaphragm and an adhesive, and negative graphite are taken as reducing agents together, and the structural part of the positive electrode material of the waste lithium battery is collapsed through reduction reaction, oxygen is released, transition metal is separated from a layered structure, and is reduced to metal oxide with low valence and magnetism, so that the magnetism of a positive electrode sheet after the waste lithium battery is broken is endowed.
On the one hand, the pyrolysis volatilizes all solvents and electrolytes in the electrolyte, electrolyte components are not contained in the pyrolyzed materials, environmental pollution caused by the electrolyte in the subsequent recovery process is avoided, and on the other hand, fluorine in the adhesive PVDF is decomposed and enters a pyrolysis gas combustion treatment system for disposal, so that the fluorine is prevented from entering the subsequent recovery process, and environmental pollution is avoided. The pyrolysis temperature is too low, the decomposition effect cannot be achieved, but the pyrolysis temperature cannot be higher than 600 ℃, so that the positive plate upper electrode powder is prevented from falling off to the greatest extent, the positive plate is kept in an intact state, the separation efficiency and the recovery rate of the positive plate and the negative plate during the subsequent strong magnetic separation are improved, and the pyrolysis temperature is lower than the melting point of metal aluminum in the positive plate so as to prevent the aluminum from being melted and then adhering positive and negative electrode materials and influence the separation efficiency. The high-temperature pyrolysis temperature is 500-600 ℃, so that the falling rate of the positive plate electrode powder can be reduced, and most of the electrode powder still adheres to the surface of the aluminum foil; and the melting point of the metal aluminum is lower than while ensuring good pyrolysis effect, and the metal is prevented from being fused and adhered with anode and cathode materials.
Further, in the step (3), the strong magnetic separation system is composed of one or more than two magnetic separators, and the magnetic induction intensity is 12000-20000 gauss; the magnetic separator is a permanent magnet magnetic separator or an electromagnetic magnetic separator.
The invention has the beneficial effects that:
(1) The recovery rate of the positive electrode powder, the negative electrode powder and the metal is above 98%, and the grade is high; the recovery process simultaneously recovers metal aluminum and copper, and the recovery utilization yield is improved by 25%; the recovery method can treat ternary lithium batteries and lithium iron phosphate batteries, is suitable for large-scale industrial production, and has extremely high economic benefit.
(2) The invention is directly electrified and crushed once without pre-discharging, thereby avoiding the pollution of self-discharging water by electrolyte and reducing the environmental protection disposal cost of the electrolyte polluted water; and the material is crushed once, the crushed material is in a large sheet shape, the size is about 30-40 mm, and the fine aluminum copper powder generated by crushing is little, so that the grade of the anode powder is not influenced. The magnetic separation, hydrodynamic separation and wet stripping are all carried out in a large sheet form in the subsequent processes; under the subsequent strong magnetic induction intensity, the large-sheet positive plate is used as a magnetic medium, so that high-gradient magnetic fields are easy to mutually adsorb, and a small amount of positive powder which is fallen off can be adsorbed by the positive plate and attached to the surface of a belt of the magnetic separator together, so that the high-efficiency separation of non-magnetic materials is realized.
(3) According to the invention, the once crushing and high-temperature pyrolytic carbon reduction processes are all under the protection of nitrogen, the generated gas is introduced into the pyrolysis gas combustion device, and purified gas is discharged after reaching the standard, so that the environmental protection of the process is improved.
(4) The invention can obtain high-grade positive electrode powder and negative electrode powder, and aluminum foil and copper foil in the waste lithium battery can be completely recovered.
Drawings
FIG. 1 is a process flow diagram of an embodiment of the present invention.
Detailed Description
The following examples are intended to further illustrate the present invention and are not intended to limit the scope of the claims.
Example 1
(1) Under the protection of nitrogen, carrying out one-stage crushing on the charged square waste ternary lithium battery, wherein the crushed materials are in a large sheet shape of 30-40 mm; the crushing process is carried out under the nitrogen atmosphere, electrolyte volatilized in the crusher is collected, and the electrolyte is sent to a pyrolysis gas combustion chamber for treatment;
(2) And (3) delivering the crushed material into a pyrolysis furnace for high-temperature carbon reduction pyrolysis, wherein the temperature is controlled at 550 ℃ for 1 hour. High-temperature pyrolysis is carried out in nitrogen atmosphere, and after electrolyte, a diaphragm and an adhesive are decomposed, waste gas is discharged to a pyrolysis gas combustion chamber for disposal;
(3) And (3) separating the weakly magnetic material and the non-magnetic material from the mixture after the carbon reduction and high-temperature pyrolysis by a strong magnetic separator under the induction magnetic field intensity of 15000 and Gao Sijiang after cooling. The weak magnetic material comprises a positive plate, positive powder, a magnetic shell and a pile head; the non-magnetic material comprises a negative plate, negative powder, a non-magnetic shell and a pile head;
(4) The magnetic mixture after magnetic separation and separation comprises a positive plate, positive plate powder, a magnetic shell and a pile head, wherein a hydrodynamic separator is added to separate the heavy shell and the pile head, the mixture of the light positive plate and the positive plate powder is stripped by a wet stripping machine, the positive plate powder on the surface of the positive plate is sieved and separated, the separated positive plate powder is dehydrated and dried to obtain the product positive plate powder and aluminum foil, the recovery rate of the positive plate powder is 98.3%, and the impurity aluminum is 0.1% and the impurity copper is 0.1%.
(5) The non-magnetic mixture selected by magnetic separation comprises a negative plate, negative powder, a non-magnetic shell and a pile head, wherein the heavy shell and the pile head are firstly selected by a hydrodynamic separator, the negative plate and the negative powder mixture is then subjected to wet stripping by a wet stripping machine, the negative powder on the surface of the negative plate is then screened and separated, the separated negative powder is dehydrated and dried, and the negative powder and copper foil are obtained, so that the recovery rate of the negative powder is 98.5%. In the recovery process, the recovery rates of aluminum and copper are 98.5 percent and 99.0 percent respectively.
Example 2
Using the crusher of the embodiment 1, crushing the charged square waste lithium iron phosphate battery at one time under the nitrogen atmosphere, wherein the crushed materials are basically 30-40 mm large-piece shaped, adding the crushed materials into an electric pyrolysis furnace for high-temperature pyrolysis, controlling the pyrolysis temperature to 570 ℃, and performing the pyrolysis for 1 hour under the nitrogen atmosphere; and (3) passing the crushed materials after pyrolysis through a strong magnetic separator, and separating a magnetic mixture and a non-magnetic mixture from each other with a magnetic induction of 15000 gauss. The weak magnetic mixture comprises a positive plate, positive plate powder, a sleeve-type shell and a pile head, wherein the magnetic mixture firstly passes through a hydrodynamic force separator to separate out a heavy magnetic shell and the pile head, the light positive plate and the positive plate powder mixture are subjected to wet stripping, the surface powder of the positive plate is stripped, and then sieving and separation are carried out, and the wet positive plate powder obtained by separation is dehydrated and dried to obtain the product positive plate powder and aluminum foil. The non-magnetic mixture comprises a negative plate, negative powder, a non-magnetic shell and a pile head, wherein the non-magnetic mixture firstly passes through a hydrodynamic force separator to separate out a heavy shell and the pile head, the light negative plate and the negative powder mixture passes through a wet stripping system to strip the surface powder of the negative plate, then is screened and separated, and the wet negative powder obtained by separation is dehydrated and dried to obtain the product negative powder and aluminum foil.
The recovery rate of the positive electrode powder is 98.8%, the recovery rate of the negative electrode powder is 98.2%, and the recovery rates of the copper foil and the aluminum foil are 98.7% and 98.8%, respectively.
Example 3
Using the crusher of the embodiment 1, crushing the charged cylindrical waste ternary lithium battery at one time under the nitrogen atmosphere, wherein the crushed material is basically in a large sheet shape of about 30mm, adding the crushed material into an electric pyrolysis furnace, and carrying out high-temperature pyrolysis at 550 ℃ for 1 hour under the nitrogen atmosphere; after pyrolysis, the crushed material is cooled to room temperature, and then the magnetic mixture and the non-magnetic mixture are separated through a strong magnetic separator with magnetic induction intensity of 17000 gauss. The magnetic mixture is firstly separated into heavy shells and pile heads through a hydrodynamic force separator, then the pole powder on the surface of the positive plate is stripped through a wet stripping system, the pole powder is sieved and separated, and the separated wet positive powder is dehydrated and dried to obtain the product positive powder and aluminum foil. Separating the non-magnetic mixture by a hydrodynamic force separator, separating the mixture of the heavy shell and the pile head, the light negative plate and the negative powder, stripping the negative powder on the surface of the negative plate by a wet stripping machine, sieving, separating, dehydrating and drying the wet negative powder obtained by separation, and obtaining the product negative powder and the copper foil.
The recovery rate of the positive electrode powder is 98.7%, the recovery rate of the negative electrode powder is 98.3%, and the recovery rates of the copper foil and the aluminum foil are 98.8% and 99.1%, respectively.
Claims (6)
1. The method for magnetically separating the anode and cathode powders from the waste lithium batteries is characterized by comprising the following steps of:
(1) Under the protection of nitrogen, a shearing crusher is adopted to crush the waste lithium batteries once, volatilized electrolyte is sent into a pyrolysis gas combustion treatment system for treatment, and the purified electrolyte reaches the discharge standard;
(2) In nitrogen atmosphere, pyrolyzing the crushed material obtained in the step (1) at 500-600 ℃, decomposing the electrolyte at high temperature to generate carbon dioxide gas, decomposing graphite in the crushed material and carbon generated by decomposing the diaphragm and the binder in the anode and the cathode to jointly serve as a carbon reducing agent, generating carbon reduction reaction with the anode material of the waste lithium battery, endowing the anode material with magnetism, and enabling the burnt waste gas to enter a pyrolysis gas combustion treatment system for treatment and be discharged after purification to reach the standard;
the carbon reduction reaction is shown in the following reaction formula:
，
(3) A strong magnetic separation system is adopted to separate magnetic materials and non-magnetic materials, wherein the magnetic materials comprise positive electrode mixed materials of positive electrode plates and positive electrode powder, a magnetic shell and a pile head, and the non-magnetic materials comprise negative electrode mixed materials of negative electrode plates and negative electrode powder, and the non-magnetic shell and the pile head;
(4) Separating the heavy magnetic shell and pile head from the magnetic materials by a hydrodynamic force separator, namely separating the light positive electrode mixed materials comprising a positive electrode plate and positive electrode powder, then stripping the positive electrode powder on the positive electrode plate by a wet stripping system, sieving, separating wet positive electrode powder and aluminum foil, dehydrating and drying the positive electrode powder to obtain product positive electrode powder, and drying the wet aluminum foil to obtain aluminum foil byproducts;
(5) Separating the non-magnetic materials into heavy shells and pile heads by a hydrodynamic force separator, namely, light negative electrode mixed materials comprising a negative electrode plate and negative electrode powder, stripping the upper electrode powder of the negative electrode plate by a wet stripping system, and sieving and separating wet negative electrode powder and copper foil; and (5) dehydrating and drying the negative electrode powder to obtain the product negative electrode powder, and drying the wet copper foil to obtain a copper foil byproduct.
2. The method for magnetically separating positive and negative electrode powder from waste lithium batteries according to claim 1, wherein the waste lithium batteries are ternary batteries or lithium iron phosphate batteries.
3. The method for magnetically separating anode and cathode powders from waste lithium batteries according to claim 1, wherein in the step (1), the waste lithium batteries are crushed into large pieces of 30-40 mm.
4. The method for magnetically separating anode and cathode powders from waste lithium batteries according to claim 1, wherein the pyrolysis temperature is 500-600 ℃; under the temperature and under the nitrogen atmosphere, carbon dioxide gas generated by the decomposition of electrolyte in the waste lithium battery, carbon generated by the decomposition of a diaphragm and an adhesive, and negative graphite are taken as reducing agents together, and the structural part of the positive electrode material of the waste lithium battery is collapsed through reduction reaction, oxygen is released, transition metal is separated from a layered structure, and is reduced to metal oxide with low valence and magnetism, so that the magnetism of a positive electrode sheet after the waste lithium battery is broken is endowed.
5. The method for magnetically separating anode and cathode powders from waste lithium batteries according to claim 1, wherein in the step (3), the strong magnetic separation system consists of one or more than two magnetic separators, and the magnetic induction intensity is 12000-20000 gauss.
6. The method for magnetically separating positive and negative electrode powder from waste lithium batteries according to claim 5, wherein the magnetic separator is a permanent magnet magnetic separator or an electromagnetic magnetic separator.
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| CN109473747A (en) * | 2018-09-11 | 2019-03-15 | 天能电池集团有限公司 | A kind of waste and old lithium ion battery dismantling recovery method |
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| CN109473747A (en) * | 2018-09-11 | 2019-03-15 | 天能电池集团有限公司 | A kind of waste and old lithium ion battery dismantling recovery method |
| CN110061320A (en) * | 2019-04-23 | 2019-07-26 | 金川集团股份有限公司 | A method of utilizing active powder material in cracking process recycling waste power lithium battery |
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