CN113611939A - Regeneration method of waste lithium ion battery electrolyte - Google Patents
Regeneration method of waste lithium ion battery electrolyte Download PDFInfo
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- CN113611939A CN113611939A CN202110888022.6A CN202110888022A CN113611939A CN 113611939 A CN113611939 A CN 113611939A CN 202110888022 A CN202110888022 A CN 202110888022A CN 113611939 A CN113611939 A CN 113611939A
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- lithium ion
- ion battery
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 60
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 42
- 239000002699 waste material Substances 0.000 title claims abstract description 32
- 238000011069 regeneration method Methods 0.000 title description 4
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000001914 filtration Methods 0.000 claims abstract description 24
- 239000012528 membrane Substances 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 230000001172 regenerating effect Effects 0.000 claims abstract description 13
- 238000000199 molecular distillation Methods 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 230000001681 protective effect Effects 0.000 claims abstract description 9
- 238000007790 scraping Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims description 62
- 239000000243 solution Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000001728 nano-filtration Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000011085 pressure filtration Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims 3
- 239000002244 precipitate Substances 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 abstract description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 239000000706 filtrate Substances 0.000 description 8
- 239000011575 calcium Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000000194 supercritical-fluid extraction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 206010016818 Fluorosis Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- IJBIBPWXYHFSRR-UHFFFAOYSA-N acetonitrile;dimethyl carbonate Chemical compound CC#N.COC(=O)OC IJBIBPWXYHFSRR-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 208000004042 dental fluorosis Diseases 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 238000012423 maintenance 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
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Images
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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4242—Regeneration of electrolyte or reactants
-
- 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
Abstract
The invention relates to the field of recovery of lithium ion battery materials, in particular to a method for regenerating a waste lithium ion battery electrolyte. According to the invention, the electrolyte is collected by adopting an organic solvent under a protective atmosphere, the metal simple substance is added into the solution to remove HF, the fluoride is generated to form a precipitate, the precipitate is removed by a filtration method, the introduced impurity metal ions are filtered by a selective filtration membrane to obtain the impurity-removed electrolyte, the added organic solvent is removed by a molecular distillation and membrane scraping way, and the missing components are supplemented according to the components of the electrolyte to obtain the regenerated electrolyte which can be directly applied to the lithium ion battery, so that the recycling is realized.
Description
Technical Field
The invention relates to the field of recovery of lithium ion battery materials, in particular to a method for regenerating a waste lithium ion battery electrolyte.
Background
Through the development of the last 30 years, the manufacturing and assembling of each component in the lithium ion battery and the use and maintenance technology of the battery are quite mature. With the increase of the usage amount of the lithium ion battery, the retirement amount of the lithium ion battery is increased. The cumulative amount of decommissioning of lithium ion power batteries, a member of lithium ion batteries, is about 8.4 to 12.4 ten thousand tons in 2019 nationwide, and is expected to exceed 73 ten thousand tons by 2025 years. Therefore, the amount of retirement of the lithium ion battery will increase greatly as the service life increases.
In a retired lithium ion battery, electrolyte is an important component of the battery and consists of a high-purity organic solvent, electrolyte and necessary additives, and during the use process of the lithium battery, the electrolyte is easily decomposed to generate LiF and PF5The electrolyte is easy to hydrolyze, and when encountering trace water, the electrolyte can be hydrolyzed to generate HF gas, while the hydrogen fluoride has great harm to plants, can be transferred and accumulated in the bodies after being absorbed, and enters human and animal bodies through food chains to cause fluorosis. The electrolyte recovery methods in the prior art mainly include an alkaline solution method, a supercritical extraction method and a vacuum distillation method, such as: in the patent CN108808156A, the solution containing the electrolyte is recovered by utilizing water immersion discharge, condensation and calcium oxide or calcium hydroxide treatment, the condensation links are more, the immersion time is long, and the efficiency is lower; patent CN110620276A uses acetone to extract and separate the electrolyte solution by supercritical extraction; the supercritical extraction condition is high in requirement, and acetone is toxic and has great harm to human bodies and the environment; the patent CN103825064A utilizes a vacuum distillation method to collect organic solvents in waste batteries; the liquid nitrogen is used for freezing and safe disassembly, so that the equipment investment cost is high, the cost burden is large, and the production practice of safety and environmental protection is not facilitated; therefore, it is urgently needed to provide a safe and environment-friendly electrolyte recovery scheme with high recovery rate and feasible exhibition at night.
Disclosure of Invention
In order to solve the problems in the prior art, the invention is based on actual industrial production, the electrolyte is collected by an organic solvent, and then the introduced impurity metal ions are removed by selective filtration after acidic substances are removed by using metals, so that the recycling of the electrolyte is realized.
In order to achieve the purpose, the invention provides a method for regenerating a waste lithium ion battery electrolyte, which comprises the following steps:
s1, cleaning and completely drying the waste lithium ion battery, then disassembling the battery under a protective atmosphere to obtain a battery shell and a core package, and cutting the core package to obtain a mixed sheet containing a positive plate, a negative plate and a diaphragm;
s2, placing the shell and the mixing sheet in an organic solvent, heating, performing ultrasonic treatment, and performing pressure filtration to obtain a mixed solution A;
s3, slowly adding a metal simple substance into the mixed solution A until the solution is neutral, and filtering to obtain a mixed solution B;
s4, filtering the mixed solution B by using a selective filter membrane to obtain a mixed solution C, and removing the organic solvent by adopting a molecular distillation and film scraping mode to obtain a mixed solution D;
and S5, measuring the components of the mixed solution D, and adding the components missing from the mixed solution according to the ratio of the components in the electrolyte to obtain the regenerated electrolyte.
Further, the organic solvent in step S2 is one or more of dimethyl carbonate (DMC), Ethylene Carbonate (EC), Propylene Carbonate (PC), absolute ethanol, methanol, N-Dimethylformamide (DMF), and acetonitrile; dimethyl carbonate is preferred.
Further, the drying temperature in the step S1 is 20 to 50 ℃.
Further, in the step S2, the solid-to-liquid ratio of the shell and the mixing piece to the organic solvent is 1: 2-10.
Further, the heating temperature in the step S2 is 20-90 ℃; the ultrasonic vibration treatment time is 0.5-10 h.
Further, the metal is any one of K, Ca, Na, Mg, Al, Zn, Fe, Sn and Pb, and is preferably Al and Ca.
Further, the selective filtering membrane is an ion nanofiltration membrane; in particular to a divalent cation membrane.
Furthermore, the temperature of the system during molecular distillation is 40-90 ℃, and the vacuum degree is 2.4-9.8 Pa.
Has the advantages that:
(1) the method comprises the steps of collecting electrolyte in the waste lithium ion battery by adopting an organic solvent under a protective atmosphere, adding a metal simple substance into a solution to remove HF, generating fluoride in the organic solvent to form a precipitate, directly removing the precipitate by a filtration method, monitoring pH in the HF removing process to ensure the HF removing effect, filtering introduced impurity metal ions by a selective filter membrane to obtain impurity-removed electrolyte, removing the redundant organic solvent by molecular distillation and membrane scraping, and supplementing actual components according to the components of the electrolyte to obtain the regenerated electrolyte which can be directly applied to the lithium ion battery, so that the cyclic utilization is realized.
(2) The reagent adopted in the regeneration method treatment process is a common organic solvent in the electrolyte, the treatment process has mild conditions, short time, safety, environmental protection, good economic benefit, high recovery rate and feasible industrial development, and is one of effective means for realizing the recycling and high-valued of the waste electrolyte.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a process flow chart of a method for regenerating a waste lithium ion battery electrolyte according to an embodiment of the present invention;
fig. 2 is a first charge-discharge curve of a battery assembled by using a regenerated electrolyte provided in an embodiment of the present invention;
FIG. 3 is a graph of the cycling performance of a cell assembled with a regenerated electrolyte as provided by an embodiment of the present invention;
fig. 4 is a comparison graph of the first discharge curves of the regenerated electrolyte assembled battery and the brand-new electrolyte assembled battery provided in the embodiment of the present invention;
fig. 5 is a comparison graph of cycle performance curves of the regenerated electrolyte assembled battery and the brand-new electrolyte assembled battery provided by the embodiment of the invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to specific embodiments, but the scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
As shown in fig. 1, an embodiment of the present invention provides a process flow diagram of a method for regenerating a waste lithium ion battery electrolyte, wherein a waste lithium battery is cleaned and dried, the battery is disassembled under a protective atmosphere to obtain a shell and a core package, the core package is crushed to obtain a mixed sheet, the shell and the mixed sheet are added with an organic solvent to be heated and ultrasonically treated to obtain a mixed solution a through pressure filtration, the pH value of the mixed solution a is 0.01-5, metal powder is added to remove HF, a fluoride precipitate is filtered to obtain a mixed solution B, a selective filtration membrane is used to filter the mixed solution B to obtain a mixed solution C, the added organic solvent is removed through molecular distillation and membrane scraping to obtain a mixed solution D, and a missing component is added through an analysis component to obtain a regenerated electrolyte.
The following examples are further illustrative.
Example 1
And (3) taking the waste lithium ion battery, cleaning the shell of the waste lithium ion battery, and completely drying the shell at 20 ℃. Disassembling the dried waste lithium ion battery in a protective atmosphere to obtain a shell and a battery core package, and randomly cutting the battery core package into pieces to obtain a mixed piece containing a positive plate, a negative plate and a diaphragm; weighing the shell and the mixing piece (marked as M), placing the shell and the mixing piece into a container, adding 2M DMC solution, heating to 50 ℃, performing ultrasonic treatment for 30min, filtering, and collecting filtrate; removing residual solid impurities in the filtrate by adopting 3-stage filter pressing to obtain a mixed solution A; adding metal calcium powder into the mixed solution A to convert HFAs precipitate CaF2Stopping the reaction when the pH value of the solution is neutral; filtering and separating CaF2Obtaining a mixed solution B; removing Ca in the mixed solution B by using a selective filtration membrane ion nanofiltration membrane2+Pure mixed solution C was obtained. And removing DMC with the mass of 2M in the mixed solution C by using a molecular distillation and film scraping device at the system temperature of 40 ℃ and the vacuum degree of 9.8Pa to obtain a mixed solution D. And testing the components of the mixed solution D, adding the missing components and the content of the mixed solution D according to the proportion of all the substances in the electrolyte, and adjusting the components of the mixed solution D to obtain the regenerated electrolyte.
Example 2:
and (3) taking the waste lithium ion battery, cleaning the shell of the waste lithium ion battery, and completely drying the shell at the temperature of 30 ℃. Disassembling the dried waste lithium ion battery in a protective atmosphere to obtain a shell and a battery core package, and randomly cutting the battery core package into pieces to obtain a mixed piece containing a positive plate, a negative plate and a diaphragm; weighing the shell and the mixed sheet (marked as M), placing the weighed shell and the mixed sheet in a container, adding an EC solution with the mass of 4M, heating to 40 ℃, performing ultrasonic treatment for 1min, filtering, and collecting filtrate; removing residual solid impurities in the filtrate by adopting 3-stage filter pressing to obtain a mixed solution A; adding aluminum metal powder to the mixed solution A to convert HF into AlF precipitate3Stopping the reaction when the pH value of the solution is neutral; filtration separation of AlF3Obtaining a mixed solution B; removing Al in the mixed solution B by using a selective filtering membrane ion nanofiltration membrane3+Pure mixed solution C was obtained. And removing EC with the mass of 4M in the mixed solution C by using a molecular distillation and film scraping device at the system temperature of 90 ℃ and the vacuum degree of 2.4Pa to obtain a mixed solution D. And testing the components of the mixed solution D, adding the missing components and the content of the mixed solution D according to the proportion of all the substances in the electrolyte, and adjusting the components of the mixed solution D to obtain the regenerated electrolyte.
Example 3
And (3) taking the waste lithium ion battery, cleaning the shell of the waste lithium ion battery, and completely drying the shell at 40 ℃. Disassembling the dried waste lithium ion battery in protective atmosphere to obtain a shell and a battery core package, and randomly cutting the battery core package into pieces to obtain the lithium ion battery with positive and negative charges,A mixed sheet of the negative electrode sheet and the separator; weighing the shell and the mixed sheet (marked as M), placing the weighed shell and the mixed sheet in a container, adding a 5M PC solution, heating to 60 ℃, performing ultrasonic treatment for 20min, filtering, and collecting filtrate; removing residual solid impurities in the filtrate by adopting 3-stage filter pressing to obtain a mixed solution A; adding metal Mg powder into the mixed solution A to convert HF into precipitate MgF2Stopping the reaction when the pH value of the solution is neutral; MgF is separated by filtration2Obtaining a mixed solution B; removing Mg in the mixed solution B by using a selective filtering membrane ion nanofiltration membrane2+Pure mixed solution C was obtained. And removing PC with the mass of 5M in the mixed solution C by using a molecular distillation and film scraping device at the system temperature of 60 ℃ and the vacuum degree of 7.3Pa to obtain a mixed solution D. And testing the components of the mixed solution D, adding the missing components and the content of the mixed solution D according to the proportion of all the substances in the electrolyte, and adjusting the components of the mixed solution D to obtain the regenerated electrolyte.
Example 4
Taking a waste lithium ion battery, cleaning the shell of the waste lithium ion battery, and completely drying the shell at 50 ℃. Disassembling the dried waste lithium ion battery in a protective atmosphere to obtain a shell and a battery core package, and randomly cutting the battery core package into pieces to obtain a mixed piece containing a positive plate, a negative plate and a diaphragm; weighing the shell and the mixed sheet (marked as M), placing the weighed shell and the mixed sheet in a container, adding 3M absolute ethyl alcohol solution, heating to 50 ℃, performing ultrasonic treatment for 3 hours, filtering, and collecting filtrate; removing residual solid impurities in the filtrate by adopting 3-stage filter pressing to obtain a mixed solution A; adding metallic calcium powder into the mixed solution A to convert HF into a precipitate CaF2Stopping the reaction when the pH value of the solution is neutral; filtering and separating CaF2Obtaining a mixed solution B; removing Ca in the mixed solution B by using a selective filtration membrane ion nanofiltration membrane2+Pure mixed solution C was obtained. And removing the 3M absolute ethyl alcohol in the mixed solution C by using a molecular distillation and film scraping device at the system temperature of 70 ℃ and the vacuum degree of 6.5Pa to obtain a mixed solution D. Testing the components of the mixed solution D, adding the missing components and the content of the mixed solution D according to the proportion of all the substances in the electrolyte, and adjusting the components of the mixed solution D to obtainAnd obtaining the regenerated electrolyte.
The regenerated electrolytes obtained in embodiments 1 to 4 of the present invention are weighed respectively, lithium iron phosphate is used as an anode, graphite is used as a cathode, and the lithium iron phosphate and the regenerated electrolytes are assembled together to form a 18650 battery, a charge-discharge curve of the battery is tested, and the cycle performance of the battery after different cycles is measured, taking the regenerated electrolyte obtained in embodiment 1 as an example, the charge-discharge curve is shown in fig. 2, and the cycle performance is shown in fig. 3.
As shown in fig. 4 and 5, when comparing the electrical properties of the electrolyte obtained by the method of the present invention with the commercial electrolyte, the specific capacity-voltage curves of the two are almost the same as the specific capacity-voltage curve of the brand new electrolyte, and meanwhile, when comparing the discharge specific capacities of the two in 100 cycles, the capacity attenuation of the two is not much different. Therefore, the electrolyte prepared by regeneration of the invention has excellent performance and extremely high commercial value.
The above-mentioned embodiments are only preferred embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical scope of the present invention, and equivalents and modifications of the technical solutions and concepts of the present invention should be covered by the scope of the present invention.
Claims (8)
1. A method for regenerating electrolyte of a waste lithium ion battery is characterized by comprising the following steps:
s1, cleaning and completely drying the waste lithium ion battery, then disassembling the battery under a protective atmosphere to obtain a battery shell and a core package, and cutting the core package to obtain a mixed sheet containing a positive plate, a negative plate and a diaphragm;
s2, placing the shell and the mixing sheet in an organic solvent, heating, performing ultrasonic treatment, and performing pressure filtration to obtain a mixed solution A;
s3, slowly adding a metal simple substance into the mixed solution A until the solution is neutral, and filtering to obtain a mixed solution B;
s4, filtering the mixed solution B by using a selective filter membrane to obtain a mixed solution C, and performing molecular distillation and membrane scraping to remove an organic solvent to obtain a mixed solution D;
and S5, measuring the components of the mixed solution D, and adding the components missing from the mixed solution according to the ratio of the components in the electrolyte to obtain the regenerated electrolyte.
2. The method for regenerating the electrolyte of the waste lithium ion battery according to claim 1, wherein the organic solvent in the step S2 is one or more of dimethyl carbonate, ethylene carbonate, propylene carbonate, absolute ethyl alcohol, methanol, N-dimethylformamide, and acetonitrile.
3. The method for regenerating the electrolyte of the waste lithium ion battery as claimed in claim 1, wherein the drying temperature in the step S1 is 20-50 ℃.
4. The method for regenerating the electrolyte of the waste lithium ion battery as claimed in claim 1, wherein the solid-to-liquid ratio of the shell and the mixed sheet to the organic solvent in the step S2 is 1: 2-10.
5. The method for regenerating the electrolyte of the waste lithium ion battery as claimed in claim 1, wherein the heating temperature in the step S2 is 20-90 ℃; the ultrasonic vibration treatment time is 0.5-10 h.
6. The method for regenerating the waste lithium ion battery electrolyte according to claim 1, wherein the metal is any one of K, Ca, Na, Mg, Al, Zn, Fe, Sn and Pb.
7. The method for regenerating the waste lithium ion battery electrolyte according to claim 1, wherein the selective filtration membrane is an ionic nanofiltration membrane.
8. The method for regenerating the electrolyte of the waste lithium ion battery according to claim 1, wherein the temperature of the system during the molecular distillation is 40-90 ℃ and the vacuum degree is 2.4-9.8 Pa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110888022.6A CN113611939A (en) | 2021-08-03 | 2021-08-03 | Regeneration method of waste lithium ion battery electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202110888022.6A CN113611939A (en) | 2021-08-03 | 2021-08-03 | Regeneration method of waste lithium ion battery electrolyte |
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