CN111900508A - Method for recycling decommissioned ternary batteries - Google Patents
Method for recycling decommissioned ternary batteries Download PDFInfo
- Publication number
- CN111900508A CN111900508A CN202010753057.4A CN202010753057A CN111900508A CN 111900508 A CN111900508 A CN 111900508A CN 202010753057 A CN202010753057 A CN 202010753057A CN 111900508 A CN111900508 A CN 111900508A
- Authority
- CN
- China
- Prior art keywords
- battery
- ternary
- frequency
- decommissioned
- recycling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000004064 recycling Methods 0.000 title claims description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010405 anode material Substances 0.000 claims abstract description 12
- 238000007599 discharging Methods 0.000 claims abstract description 5
- 238000012216 screening Methods 0.000 claims abstract description 5
- 230000010355 oscillation Effects 0.000 claims description 32
- 238000002386 leaching Methods 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 24
- 238000012545 processing Methods 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 230000005672 electromagnetic field Effects 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000020477 pH reduction Effects 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 230000008929 regeneration Effects 0.000 claims description 4
- 238000011069 regeneration method Methods 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 25
- 230000008901 benefit Effects 0.000 abstract description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007774 positive electrode material Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000005272 metallurgy Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000009388 chemical precipitation 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
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using 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
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a method for recovering a decommissioned ternary battery, which is characterized by comprising the following steps of: step S1, discharging, disassembling and sorting; step S2, recovering the shell and the diaphragm; step S3, carrying out high-temperature treatment on the battery negative plate, and then screening the battery negative plate; and step S4, recovering the battery positive plate by combining different-frequency electromagnetic treatment and microwave treatment with an organic solvent. The recovery method of the retired ternary battery disclosed by the invention is short in process flow, simple to operate, capable of safely, environmentally, quickly and efficiently recovering the ternary battery, effectively reducing the battery sorting cost, improving the recovery economic benefit and realizing high recovery rate and high-grade selective recovery of lithium element in the ternary battery anode material.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a method for recycling a retired ternary battery.
Background
The lithium ion battery is favored by markets and consumers due to the advantages of high energy density, long cycle life, environmental friendliness and the like, and is widely applied to the fields of mobile electronic equipment, electric automobiles, reserve power supplies and the like. At present, two types of lithium batteries are mainly reserved in the market, one type is a lithium iron phosphate (LFP) battery as a positive electrode material, and the other type is a ternary battery. The ternary battery is also called a ternary polymer lithium battery, and is a lithium battery of a ternary positive electrode material using lithium Nickel Cobalt Manganese (NCM) or lithium Nickel Cobalt Aluminate (NCA) as a positive electrode material, and the battery has the advantages of high energy density, high voltage, good cycle performance and safe operation, is particularly suitable for the power requirement of a new energy automobile, is widely applied, and greatly promotes the development of the new energy automobile. With the development of new energy electric vehicles, the production capacity of the ternary battery and the number of the retired ternary battery are also continuously increased. Toxic substances in the retired ternary batteries are difficult to degrade, the waste batteries are discarded randomly to seriously pollute soil and underground water, and the toxic gas is dissipated by arbitrarily burning the waste batteries. Therefore, how to effectively recycle the retired ternary battery is an urgent problem to be solved by those skilled in the art, and is a necessary requirement for a sustainable development path.
The existing ternary battery recovery method mainly comprises two categories of chemical metallurgy and high-temperature metallurgy. The chemical metallurgy method adopts a series of process methods such as mechanical crushing, acid-base leaching, impurity removal, extraction and the like, a large amount of chemicals are consumed, a large amount of acid-base waste liquid is generated and needs to be further subjected to post-treatment, and the use of strong acid and strong base also causes that the method is difficult to realize large-scale treatment. The pyrometallurgical method carries out recovery treatment through processes such as mechanical crushing, high-temperature incineration, fragment disassembly, residue/metal/recovery, tail gas treatment and the like, but the process has very high requirements on treatment equipment, and a large amount of toxic gas is discharged, thereby bringing great pressure to environmental protection. In a word, the existing recovery method of the retired ternary battery generally has the problems of very high energy consumption, complex process, a plurality of impurities in the separated ternary cathode material and the like.
The Chinese patent with application publication number CN106505272A discloses a method for treating waste materials of positive electrode materials of lithium batteries, which comprises the following steps: roasting A, acidifying and leaching B, removing iron and aluminum C, removing copper and zinc D, fluorinating and precipitating lithium E, removing calcium and magnesium F, extracting G in multiple stages, removing oil H and the like; the method improves the leaching efficiency by adding hydrogen peroxide as a reducing agent, and then separates lithium, nickel, cobalt and manganese by chemical precipitation and solvent extraction; the process is complex, the cost of the reducing agent is high, the subsequent separation and purification procedures are various and complex, and meanwhile, the solution after separation and purification has low concentration of valuable metals and can generate a large amount of wastewater.
Therefore, it is very important to develop a recycling method for the decommissioned ternary battery, which can safely, environmentally, quickly and efficiently recycle the ternary battery, effectively reduce the battery sorting cost and improve the recycling economic benefit.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a recovery method of a decommissioned ternary battery, which has the advantages of short process flow, simple operation, safety, environmental protection, rapidness and high efficiency in recovering the ternary battery, can effectively reduce the battery sorting cost, improves the recovery economic benefit, and can realize high recovery rate and high grade selective recovery of lithium element in the ternary battery anode material.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for recycling a decommissioned ternary battery is characterized by comprising the following steps:
s1, placing the retired ternary battery in a circulating salt solution for discharging for 50-60 hours, and then naturally airing for 40-50 hours; then disassembling the discharged decommissioned ternary battery in a closed disassembling workshop by using automatic crushing and sorting equipment, conveying the crushed battery material to a hydraulic separator, and separating to obtain a shell, a diaphragm, a battery positive plate and a battery negative plate;
step S2, washing and drying the sorted shells in sequence, and then sending the shells to a lithium battery manufacturer for reuse; cleaning the sorted diaphragm with saturated sodium chloride aqueous solution, and then sequentially carrying out acidification dissolution, rinsing and drying on the diaphragm for industrial regeneration products; respectively soaking the battery positive plate and the battery negative plate in an organic leaching solvent for leaching, filtering after leaching is finished, drying filter residues, distilling filtrate, recovering the organic leaching solvent for recycling other ternary batteries, and supplying lithium salt obtained by distillation for industrial use;
step S3, performing high-temperature treatment on the battery negative plate obtained through the treatment in the step S2, and then screening the battery negative plate to obtain a current collector and negative electrode material powder which can be directly used as a raw material to produce a lithium ion battery negative electrode material;
step S4, mixing the battery positive plate obtained through the processing of the step S2 with an organic solvent, placing the mixture in a low-frequency electromagnetic oscillation field, and processing the mixture for 15 to 20 minutes in the electromagnetic field; then processing in a high-frequency electromagnetic oscillation field for 3-6 minutes; finally, processing for 8-15 minutes in an equal frequency range; then placing the mixture in a microwave field for microwave treatment for 15-25 minutes; and then sorting out a current collector, removing the solvent from the residual substances through rotary evaporation, pressing the residual substances into a filter cake by using a filter press, and finally sintering the filter cake at the temperature of 700-950 ℃, wherein the filter cake can be directly used as a raw material to produce the lithium ion battery anode material.
Preferably, the salt solution in step S1 is at least one of a sodium sulfate solution, a sodium chloride solution, and an ammonium chloride solution.
Preferably, the salt solution in the step S1 has a mass percentage concentration of 0.5-2.5%.
Preferably, the organic leaching solvent in step S2 is at least one of diethyl carbonate, N-dimethylformamide, tetrahydrofuran and ethyl methyl carbonate.
Preferably, the bath ratio of the battery positive plate to the organic leaching solvent in the step S2 is 1 (5-10); the bath ratio of the battery negative plate to the organic leaching solvent is 1 (4-8).
Preferably, the temperature of the high temperature treatment in step S3 is 650-950 ℃.
Preferably, the organic solvent in step S4 is at least one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and propylene carbonate.
Preferably, the mass ratio of the battery positive plate to the organic solvent in the step S4 is 1 (5-10).
Preferably, in step S4, the frequency of the low-frequency electromagnetic oscillation field is 5 to 12HZ, and the medium-low duty ratio is 20 to 40% at this time; the frequency of the high-frequency electromagnetic oscillation field is 30-52HZ, and the medium-low duty ratio is 10-30% at the moment; the frequency of the constant frequency electromagnetic oscillation field is 13-30HZ, and the duty ratio of the medium-low duty ratio is 20-30%.
Preferably, the microwave frequency in step S4 is 100GHZ-300 GHZ.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the recovery method for the retired ternary battery provided by the invention is short in process flow, simple to operate, capable of safely, environmentally, quickly and efficiently recovering the ternary battery, effectively reducing the battery sorting cost, improving the recovery economic benefit, and capable of realizing high recovery rate and high-grade selective recovery of lithium in the ternary battery anode material. By utilizing different-frequency electromagnetic treatment and microwave treatment, the recovery rate of the anode material can be effectively improved, and the anode material can be activated and regenerated.
Detailed Description
The following detailed description of preferred embodiments of the invention will be made.
A method for recycling a decommissioned ternary battery is characterized by comprising the following steps:
s1, placing the retired ternary battery in a circulating salt solution for discharging for 50-60 hours, and then naturally airing for 40-50 hours; then disassembling the discharged decommissioned ternary battery in a closed disassembling workshop by using automatic crushing and sorting equipment, conveying the crushed battery material to a hydraulic separator, and separating to obtain a shell, a diaphragm, a battery positive plate and a battery negative plate;
step S2, washing and drying the sorted shells in sequence, and then sending the shells to a lithium battery manufacturer for reuse; cleaning the sorted diaphragm with saturated sodium chloride aqueous solution, and then sequentially carrying out acidification dissolution, rinsing and drying on the diaphragm for industrial regeneration products; respectively soaking the battery positive plate and the battery negative plate in an organic leaching solvent for leaching, filtering after leaching is finished, drying filter residues, distilling filtrate, recovering the organic leaching solvent for recycling other ternary batteries, and supplying lithium salt obtained by distillation for industrial use;
step S3, performing high-temperature treatment on the battery negative plate obtained through the treatment in the step S2, and then screening the battery negative plate to obtain a current collector and negative electrode material powder which can be directly used as a raw material to produce a lithium ion battery negative electrode material;
step S4, mixing the battery positive plate obtained through the processing of the step S2 with an organic solvent, placing the mixture in a low-frequency electromagnetic oscillation field, and processing the mixture for 15 to 20 minutes in the electromagnetic field; then processing in a high-frequency electromagnetic oscillation field for 3-6 minutes; finally, processing for 8-15 minutes in an equal frequency range; then placing the mixture in a microwave field for microwave treatment for 15-25 minutes; and then sorting out a current collector, removing the solvent from the residual substances through rotary evaporation, pressing the residual substances into a filter cake by using a filter press, and finally sintering the filter cake at the temperature of 700-950 ℃, wherein the filter cake can be directly used as a raw material to produce the lithium ion battery anode material.
Preferably, the salt solution in step S1 is at least one of a sodium sulfate solution, a sodium chloride solution, and an ammonium chloride solution.
Preferably, the salt solution in the step S1 has a mass percentage concentration of 0.5-2.5%.
Preferably, the organic leaching solvent in step S2 is at least one of diethyl carbonate, N-dimethylformamide, tetrahydrofuran and ethyl methyl carbonate.
Preferably, the bath ratio of the battery positive plate to the organic leaching solvent in the step S2 is 1 (5-10); the bath ratio of the battery negative plate to the organic leaching solvent is 1 (4-8).
Preferably, the temperature of the high temperature treatment in step S3 is 650-950 ℃.
Preferably, the organic solvent in step S4 is at least one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and propylene carbonate.
Preferably, the mass ratio of the battery positive plate to the organic solvent in the step S4 is 1 (5-10).
Preferably, in step S4, the frequency of the low-frequency electromagnetic oscillation field is 5 to 12HZ, and the medium-low duty ratio is 20 to 40% at this time; the frequency of the high-frequency electromagnetic oscillation field is 30-52HZ, and the medium-low duty ratio is 10-30% at the moment; the frequency of the constant frequency electromagnetic oscillation field is 13-30HZ, and the duty ratio of the medium-low duty ratio is 20-30%.
Preferably, the microwave frequency in step S4 is 100GHZ-300 GHZ.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the recovery method for the retired ternary battery provided by the invention is short in process flow, simple to operate, capable of safely, environmentally, quickly and efficiently recovering the ternary battery, effectively reducing the battery sorting cost, improving the recovery economic benefit, and capable of realizing high recovery rate and high-grade selective recovery of lithium in the ternary battery anode material. By utilizing different-frequency electromagnetic treatment and microwave treatment, the recovery rate of the anode material can be effectively improved, and the anode material can be activated and regenerated.
The invention will be further described with reference to specific examples, but the scope of protection of the invention is not limited thereto:
example 1
Embodiment 1 provides a method for recycling a decommissioned ternary battery, which is characterized by comprising the following steps:
s1, placing the decommissioned ternary battery in a circulating salt solution for discharging for 50 hours, and then naturally drying for 40 hours; then disassembling the discharged decommissioned ternary battery in a closed disassembling workshop by using automatic crushing and sorting equipment, conveying the crushed battery material to a hydraulic separator, and separating to obtain a shell, a diaphragm, a battery positive plate and a battery negative plate;
step S2, washing and drying the sorted shells in sequence, and then sending the shells to a lithium battery manufacturer for reuse; cleaning the sorted diaphragm with saturated sodium chloride aqueous solution, and then sequentially carrying out acidification dissolution, rinsing and drying on the diaphragm for industrial regeneration products; respectively soaking the battery positive plate and the battery negative plate in an organic leaching solvent for leaching, filtering after leaching is finished, drying filter residues, distilling filtrate, recovering the organic leaching solvent for recycling other ternary batteries, and supplying lithium salt obtained by distillation for industrial use;
step S3, performing high-temperature treatment on the battery negative plate obtained through the treatment in the step S2, and then screening the battery negative plate to obtain a current collector and negative electrode material powder which can be directly used as a raw material to produce a lithium ion battery negative electrode material;
step S4, mixing the battery positive plate obtained through the processing of the step S2 with an organic solvent, placing the mixture in a low-frequency electromagnetic oscillation field, and processing the mixture for 15 minutes in the electromagnetic field; then processing for 3 minutes in a high-frequency electromagnetic oscillation field; finally, processing for 8 minutes in an equal frequency range; then placing the mixture in a microwave field for microwave treatment for 15 minutes; and then sorting out a current collector, removing the solvent from the residual substances through rotary evaporation, pressing the residual substances into a filter cake by using a filter press, and finally sintering the filter cake at 700 ℃ to directly serve as a raw material to produce the lithium ion battery anode material.
In the step S1, the salt solution is at least one of a sodium sulfate solution, a sodium chloride solution and an ammonium chloride solution; the mass percentage concentration of the salt solution in the step S1 is 0.5%.
In step S2, the organic leaching solvent is diethyl carbonate; in the step S2, the bath ratio of the battery positive plate to the organic leaching solvent is 1: 5; the bath ratio of the battery negative plate to the organic leaching solvent is 1: 4.
The temperature of the high-temperature treatment in step S3 was 650 ℃.
In the step S4, the organic solvent is N-methyl pyrrolidone; the mass ratio of the battery positive plate to the organic solvent is 1: 5; in the step S4, the frequency of the low-frequency electromagnetic oscillation field is 5HZ, and at this time, the medium-low duty ratio is 40%; the frequency of the high-frequency electromagnetic oscillation field is 52HZ, and the medium-low duty ratio is 30% at the moment; the frequency of the constant-frequency electromagnetic oscillation field is 30HZ, and the medium-low duty ratio is 30% at the moment; the microwave frequency is 100 GHz.
Example 2
Embodiment 2 provides a method for recycling an ex-service ternary battery, which is substantially the same as embodiment 1, except that in step S4, the frequency of the low-frequency electromagnetic oscillation field is 7HZ, and at this time, the medium-low duty ratio is 25%; the frequency of the high-frequency electromagnetic oscillation field is 33HZ, and the medium-low duty ratio is 15% at the moment; the frequency of the constant-frequency electromagnetic oscillation field is 17HZ, and the medium-low duty ratio is 22% at the moment; the microwave frequency is 150 GHz.
Example 3
Embodiment 3 provides a method for recycling an ex-service ternary battery, which is substantially the same as embodiment 1, except that in step S4, the frequency of the low-frequency electromagnetic oscillation field is 9HZ, and at this time, the medium-low duty ratio is 30%; the frequency of the high-frequency electromagnetic oscillation field is 45HZ, and the medium-low duty ratio is 20% at the moment; the frequency of the constant-frequency electromagnetic oscillation field is 23HZ, and the medium-low duty ratio is 25% at the moment; the microwave frequency is 200 GHZ.
Example 4
Embodiment 4 provides a method for recycling an ex-service ternary battery, which is substantially the same as embodiment 1, except that in step S4, the frequency of the low-frequency electromagnetic oscillation field is 11HZ, and at this time, the medium-low duty ratio is 38%; the frequency of the high-frequency electromagnetic oscillation field is 50HZ, and the medium-low duty ratio is 28% at the moment; the frequency of the constant-frequency electromagnetic oscillation field is 27HZ, and the medium-low duty ratio is 28% at the moment; the microwave frequency is 280 GHZ.
Example 5
Embodiment 5 provides a method for recycling an ex-service ternary battery, which is substantially the same as embodiment 1, except that in step S4, the frequency of the low-frequency electromagnetic oscillation field is 12HZ, and at this time, the medium-low duty ratio is 40%; the frequency of the high-frequency electromagnetic oscillation field is 52HZ, and the medium-low duty ratio is 30% at the moment; the frequency of the constant-frequency electromagnetic oscillation field is 30HZ, and the medium-low duty ratio is 30% at the moment; the microwave frequency is 300 GHZ.
Comparative example 1
Comparative example 1 provides a method of recycling a decommissioned ternary battery, which is substantially the same as example 1, except that there is no low frequency electromagnetic treatment.
Comparative example 2
Comparative example 2 provides a method of recycling a decommissioned ternary battery, which is substantially the same as example 1, except that there is no high frequency electromagnetic treatment.
Comparative example 3
Comparative example 3 provides a method of recycling a decommissioned ternary battery, which is substantially the same as example 1, except that there is no microwave treatment.
In order to further illustrate the beneficial technical effects of the invention, the recovery rate statistics of the lithium element recovered by the recovery method of the retired ternary battery in the embodiment of the invention are carried out, and the results are shown in table 1.
TABLE 1
| Item | Recovery ratio of lithium (%) |
| Example 1 | 97.9 |
| Example 2 | 98.3 |
| Example 3 | 98.8 |
| Example 4 | 99.2 |
| Example 5 | 99.5 |
| Comparative example 1 | 93.7 |
| Comparative example 2 | 93.5 |
| Comparative example 3 | 94.1 |
As can be seen from table 1, the method for recycling the active ternary battery disclosed in the embodiment of the present invention has a better recycling effect, which is a result of the synergistic effect of the process steps.
The above-mentioned embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (10)
1. A method for recycling a decommissioned ternary battery is characterized by comprising the following steps:
s1, placing the retired ternary battery in a circulating salt solution for discharging for 50-60 hours, and then naturally airing for 40-50 hours; then disassembling the discharged decommissioned ternary battery in a closed disassembling workshop by using automatic crushing and sorting equipment, conveying the crushed battery material to a hydraulic separator, and separating to obtain a shell, a diaphragm, a battery positive plate and a battery negative plate;
step S2, washing and drying the sorted shells in sequence, and then sending the shells to a lithium battery manufacturer for reuse; cleaning the sorted diaphragm with saturated sodium chloride aqueous solution, and then sequentially carrying out acidification dissolution, rinsing and drying on the diaphragm for industrial regeneration products; respectively soaking the battery positive plate and the battery negative plate in an organic leaching solvent for leaching, filtering after leaching is finished, drying filter residues, distilling filtrate, recovering the organic leaching solvent for recycling other ternary batteries, and supplying lithium salt obtained by distillation for industrial use;
step S3, performing high-temperature treatment on the battery negative plate obtained through the treatment in the step S2, and then screening the battery negative plate to obtain a current collector and negative electrode material powder which can be directly used as a raw material to produce a lithium ion battery negative electrode material;
step S4, mixing the battery positive plate obtained through the processing of the step S2 with an organic solvent, placing the mixture in a low-frequency electromagnetic oscillation field, and processing the mixture for 15 to 20 minutes in the electromagnetic field; then processing in a high-frequency electromagnetic oscillation field for 3-6 minutes; finally, processing for 8-15 minutes in an equal frequency range; then placing the mixture in a microwave field for microwave treatment for 15-25 minutes; and then sorting out a current collector, removing the solvent from the residual substances through rotary evaporation, pressing the residual substances into a filter cake by using a filter press, and finally sintering the filter cake at the temperature of 700-950 ℃, wherein the filter cake can be directly used as a raw material to produce the lithium ion battery anode material.
2. The method of claim 1, wherein the salt solution in step S1 is at least one of a sodium sulfate solution, a sodium chloride solution and an ammonium chloride solution.
3. The method of claim 1, wherein the salt solution is used in a concentration of 0.5-2.5% by mass in step S1.
4. The method of claim 1, wherein the organic leaching solvent in step S2 is at least one of diethyl carbonate, N-dimethylformamide, tetrahydrofuran and ethyl methyl carbonate.
5. The method for recycling the decommissioned ternary battery according to claim 1, wherein the bath ratio of the battery positive plate to the organic leaching solvent in the step S2 is 1 (5-10); the bath ratio of the battery negative plate to the organic leaching solvent is 1 (4-8).
6. The method as claimed in claim 1, wherein the temperature of the high temperature treatment in step S3 is 650-950 ℃.
7. The method of claim 1, wherein the organic solvent in step S4 is at least one of N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide and propylene carbonate.
8. The method for recycling the decommissioned ternary battery according to claim 1, wherein the mass ratio of the battery positive plate to the organic solvent in the step S4 is 1 (5-10).
9. The recycling method of decommissioned ternary batteries according to claim 1, wherein in step S4, the frequency of the low-frequency electromagnetic oscillation field is 5 to 12HZ, and the medium-low duty ratio is 20 to 40% at this time; the frequency of the high-frequency electromagnetic oscillation field is 30-52HZ, and the medium-low duty ratio is 10-30% at the moment; the frequency of the constant frequency electromagnetic oscillation field is 13-30HZ, and the duty ratio of the medium-low duty ratio is 20-30%.
10. The method as claimed in claim 1, wherein the microwave frequency in step S4 is 100GHZ-300 GHZ.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010753057.4A CN111900508A (en) | 2020-07-30 | 2020-07-30 | Method for recycling decommissioned ternary batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010753057.4A CN111900508A (en) | 2020-07-30 | 2020-07-30 | Method for recycling decommissioned ternary batteries |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111900508A true CN111900508A (en) | 2020-11-06 |
Family
ID=73182665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010753057.4A Pending CN111900508A (en) | 2020-07-30 | 2020-07-30 | Method for recycling decommissioned ternary batteries |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111900508A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112687974A (en) * | 2021-03-16 | 2021-04-20 | 嘉兴模度新能源有限公司 | Chemical disassembling method applied to battery adhesive module |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102355960A (en) * | 2009-04-07 | 2012-02-15 | 川崎重工业株式会社 | Apparatus and method for cleaning thin film solar cell panel by jetting high-pressure liquid |
| CN105576317A (en) * | 2016-01-27 | 2016-05-11 | 广州宝狮无线供电技术有限公司 | Program-controlled electromagnetic induction heating device and method for processing waste battery by using device |
| CN105870529A (en) * | 2016-05-03 | 2016-08-17 | 深圳市沃特玛电池有限公司 | Recovery method for waste lithium ion batteries |
| CN105925807A (en) * | 2016-05-26 | 2016-09-07 | 广东新生环保科技股份有限公司 | Recycling process of waste battery lead |
| US20170207443A1 (en) * | 2016-01-18 | 2017-07-20 | GRST Energy Limited | Method of preparing battery electrodes |
| CN110240339A (en) * | 2019-06-05 | 2019-09-17 | 深圳市银河联邦科技文化有限公司 | Processing method, device and the computer readable storage medium of sewage |
| CN209804839U (en) * | 2019-05-16 | 2019-12-17 | 山东锂想新能源科技有限公司 | Device of electromagnetic pyrolysis retired lithium battery |
| CN110643816A (en) * | 2019-09-16 | 2020-01-03 | 浙江省冶金研究院有限公司 | Method for recovering lithium from waste ternary lithium battery |
| CN110931909A (en) * | 2019-11-14 | 2020-03-27 | 珠海格力绿色再生资源有限公司 | Recovery method of waste lithium ion battery |
-
2020
- 2020-07-30 CN CN202010753057.4A patent/CN111900508A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102355960A (en) * | 2009-04-07 | 2012-02-15 | 川崎重工业株式会社 | Apparatus and method for cleaning thin film solar cell panel by jetting high-pressure liquid |
| US20170207443A1 (en) * | 2016-01-18 | 2017-07-20 | GRST Energy Limited | Method of preparing battery electrodes |
| CN105576317A (en) * | 2016-01-27 | 2016-05-11 | 广州宝狮无线供电技术有限公司 | Program-controlled electromagnetic induction heating device and method for processing waste battery by using device |
| CN105870529A (en) * | 2016-05-03 | 2016-08-17 | 深圳市沃特玛电池有限公司 | Recovery method for waste lithium ion batteries |
| CN105925807A (en) * | 2016-05-26 | 2016-09-07 | 广东新生环保科技股份有限公司 | Recycling process of waste battery lead |
| CN209804839U (en) * | 2019-05-16 | 2019-12-17 | 山东锂想新能源科技有限公司 | Device of electromagnetic pyrolysis retired lithium battery |
| CN110240339A (en) * | 2019-06-05 | 2019-09-17 | 深圳市银河联邦科技文化有限公司 | Processing method, device and the computer readable storage medium of sewage |
| CN110643816A (en) * | 2019-09-16 | 2020-01-03 | 浙江省冶金研究院有限公司 | Method for recovering lithium from waste ternary lithium battery |
| CN110931909A (en) * | 2019-11-14 | 2020-03-27 | 珠海格力绿色再生资源有限公司 | Recovery method of waste lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| 吉效科: "《设备质量控制概论 第1版》", 31 December 2017 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112687974A (en) * | 2021-03-16 | 2021-04-20 | 嘉兴模度新能源有限公司 | Chemical disassembling method applied to battery adhesive module |
| CN112687974B (en) * | 2021-03-16 | 2021-06-18 | 嘉兴模度新能源有限公司 | Chemical disassembling method applied to battery adhesive module |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI726033B (en) | Process for recovering metal values from spent lithium ion batteries with high manganese content | |
| FI3517641T4 (en) | Procedure for utilization of lithium batteries | |
| CN112813270B (en) | Method for recycling waste nickel-cobalt-manganese ternary lithium battery anode material | |
| CA2992019A1 (en) | A method of recovering metals from spent li-ion batteries | |
| CN107623152B (en) | Resource recovery method of waste lithium-ion power battery | |
| CN113904018B (en) | Method for preparing active negative electrode material by recycling battery powder leaching slag | |
| CN110468281A (en) | Valuable metal separation and recovery method in a kind of waste and old cobalt acid lithium battery | |
| US20210050634A1 (en) | Method for recycling lithium-ion batteries | |
| CN106299526A (en) | Recycling method of strong alkali solution in waste lithium battery recycling industry | |
| CN117477082A (en) | A method for reusing scrapped lithium-ion battery negative electrode materials | |
| CN116199202A (en) | Method for recycling and preparing battery-grade ferric phosphate from ferric phosphate slag | |
| CN111900507A (en) | Method for recycling retired lithium iron phosphate battery | |
| CN119546789A (en) | How to deal with waste batteries | |
| CN111321297A (en) | A method for recovering valuable metals from spent lithium-ion batteries | |
| CN117144139B (en) | Method for extracting cobalt from waste ternary lithium ion battery | |
| CN113603120A (en) | Method for recovering battery-grade lithium from waste lithium iron phosphate through short-process acid leaching | |
| CN111900508A (en) | Method for recycling decommissioned ternary batteries | |
| CN116683082B (en) | Microwave-assisted pyrogenic process-wet process combined process recovery method for waste lithium batteries | |
| CN112820970A (en) | Harmless treatment method for waste lithium battery electrolyte | |
| CN109777957B (en) | Solvent composition suitable for leaching and separating waste lithium battery material and leaching and separating method | |
| WO2024079705A1 (en) | A method to obtain pure graphite from leach residue of spent lithium-ion batteries | |
| CN115072751B (en) | Method for preparing low-fluorine lithium carbonate by recycling lithium iron phosphate battery | |
| CN111129634A (en) | Method for separating and recovering anode material of failed ternary lithium ion battery | |
| CN117383557A (en) | A method for purifying and removing impurities from acid-leached graphite residue of waste lithium battery materials | |
| IL319141A (en) | Method for reconditioning lithium-containing energy accumulators |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201106 |