CN112599879A - Lithium ion battery recovery method - Google Patents
Lithium ion battery recovery method Download PDFInfo
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- CN112599879A CN112599879A CN202011474696.3A CN202011474696A CN112599879A CN 112599879 A CN112599879 A CN 112599879A CN 202011474696 A CN202011474696 A CN 202011474696A CN 112599879 A CN112599879 A CN 112599879A
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- lithium ion
- ion battery
- water
- electrode material
- lithium
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- 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
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- 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
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- 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
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- 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 application provides a lithium ion battery recovery method, which comprises the following steps: removing the aluminum-plastic film shell of the charged lithium ion battery in an inert gas environment, and separating out a positive electrode material, a negative electrode material and a diaphragm; reacting the negative electrode material with water to obtain a lithium hydroxide solution, and separating graphite and a copper foil current collector; reacting the positive electrode material with an alkali solution, and filtering to obtain ferric hydroxide precipitate; and mixing the phosphate filtrate with the lithium hydroxide solution for reaction to generate lithium phosphate precipitate and alkali. The method can effectively recover valuable elements such as Li, Fe and the like, and control environment harmful elements such as P and the like.
Description
Technical Field
The application relates to a lithium ion battery recycling method.
Background
The lithium ion battery has the advantages of high energy density, less self-discharge, long cycle life, environmental friendliness and the like, and is the main development direction in the development of clean energy in the 21 st century. Currently, lithium ion batteries have been widely used in mobile electronic devices, electric vehicles, and other large energy storage devices. However, lithium ion batteries have a limited lifetime and are out of service and contain large amounts of valuable metal elements and environmentally harmful substances. The development of a method for efficiently recovering lithium ion batteries is imminent.
Due to the complex material system, complex structure and flammability of lithium ion batteries, the method for efficiently recycling lithium ion batteries still has great challenges. In the process of implementing the invention, the inventor finds that valuable metal elements and environmentally harmful phosphorus and fluorine elements are enriched in more than 10 materials, and resource waste and environmental pollution are caused if the valuable metal elements and the environmentally harmful phosphorus and fluorine elements cannot be effectively recovered. In addition, the inventor also finds that the recycled battery often has certain electric quantity, a fire event is easy to occur when the battery is disassembled in the air, if the battery is discharged and recycled, certain influence is caused on the environment, and the discharged electrode material is in a stable state and is not beneficial to recycling. The existing wet method and fire method strategies have low separation efficiency and high energy consumption, generate a large amount of waste residues, waste liquid and gas to be discharged, and are difficult to realize the circular economy of the lithium ion battery.
Disclosure of Invention
In view of the above, it is necessary to provide a method for recovering lithium ion batteries, which can not only separate the battery components, but also effectively recover valuable elements such as Li and Fe and control harmful elements such as P.
The lithium ion battery recycling method comprises the following steps: removing the aluminum-plastic film shell of the charged lithium ion battery in an inert gas environment, and separating out a positive electrode material, a negative electrode material and a diaphragm; reacting the negative electrode material with water to obtain a lithium hydroxide solution, and separating graphite and a copper foil current collector; reacting the positive electrode material with an alkali solution, and filtering to obtain ferric hydroxide precipitate; and mixing the phosphate filtrate with the lithium hydroxide solution for reaction to generate lithium phosphate precipitate and alkali.
Optionally, the method further comprises: and charging the lithium ion battery to a voltage V1 by using a current I1 constant current, and then charging to a current I2 by using a voltage V2 constant voltage.
Alternatively, I1 ═ 2A, V1 ═ V2 ═ 4V, and I2 ═ 0.02A.
Optionally, the water is industrial water, domestic water, deionized water, ultrapure water, or high temperature water vapor.
Optionally, the water comprises ethanol.
Optionally, the water contains a salt.
Optionally, the alkali solution is sodium hydroxide, potassium hydroxide, or ammonia.
Optionally, the inert gas is argon.
According to the lithium ion battery recovery method provided by the embodiment of the application, not only can each component of the battery be separated independently, but also valuable elements such as Li and Fe can be effectively recovered, and environmentally harmful elements such as P can be controlled. The application can promote the industrialization of the recovery of all types of lithium ion batteries.
Drawings
Fig. 1 is a flowchart of a lithium ion battery recycling method according to an embodiment of the present application.
Fig. 2 is a view showing a situation in which the charged battery is exposed to the air to open the case, and smoke and fire rapidly occur.
The following detailed description will explain the present application in further detail in conjunction with the above-described figures.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments of the present application. Additionally, the endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Fig. 1 is a flowchart illustrating a method for recycling a lithium ion battery according to an embodiment of the present disclosure. The order of the steps in the flow chart may be changed and some steps may be omitted according to different needs. The lithium ion battery recycling method may include the steps of:
and step S1, removing the aluminum-plastic film shell of the charged lithium ion battery in an inert gas environment, and separating out the anode material, the cathode material, the diaphragm and the shell.
In this embodiment, the lithium ion battery may be any type of battery to be recovered with any capacity.
For example, the lithium ion battery may be a lithium iron phosphate (LFP) battery, a Lithium Nickel Oxide (LNO) battery, a Lithium Manganese Oxide (LMO) battery, a Lithium Cobalt Oxide (LCO) battery, a nickel cobalt manganese ternary lithium (NCM) battery, a nickel cobalt aluminum ternary lithium (NCA) battery.
In one embodiment, the inert gas is argon.
In this embodiment, before the lithium ion battery is placed in the inert gas environment, the lithium ion battery may be charged with a constant current of current I1 to a voltage V1, and then charged with a constant voltage of voltage V2 to a current of I2.
Preferably, I1 ═ 2A, V1 ═ V2 ═ 4V, and I2 ═ 0.02A.
For example, a 4.6Ah soft-package lithium iron phosphate battery is first charged to 4V at a constant current of 2A, then charged to 0.02A at a constant voltage of 4V, and then the charged soft-package lithium iron phosphate battery is placed in a glove box in an argon atmosphere to remove an aluminum-plastic film shell, and then the soft-package lithium iron phosphate battery is unwound and wound to separate a positive electrode material, a negative electrode material, a diaphragm and a shell.
It should be noted that the inventors also performed a test in which the lithium ion battery was opened in air. Referring to fig. 2, the test shows that the 4.6Ah charged battery was left open in air for about 1 minute, started to smoke and started to fire rapidly.
Compared with the case that the lithium ion battery is opened in the air, the case that the aluminum-plastic film is removed from the charged lithium ion battery in the inert gas environment is avoided, and the case is safer.
And step S2, reacting the negative electrode material with water to obtain a lithium hydroxide (LiOH) solution, and separating graphite and a copper foil current collector.
The main component of the negative electrode material includes a golden active lithium carbon compound LiCx(e.g., LiC)6). Therefore, when the negative electrode material reacts with the water, lithium hydroxide is generated, and the lithium hydroxide solution is obtained after the lithium hydroxide is dissolved in the water. Meanwhile, the graphite in the negative electrode material can be separated out and the copper foil current collector in the negative electrode material can be completely recycled after the graphite in the negative electrode material sinks to the bottom of water.
In this embodiment, the water reacted with the anode material may be industrial water, domestic water, deionized water, ultrapure water, or high-temperature water vapor. In one embodiment, the water may contain a solution such as ethanol. In other embodiments, the water may also contain a salt such as lithium hydroxide.
Step S3, reacting the positive electrode material with an alkali solution, and filtering to obtain ferric hydroxide (Fe (OH)3) Precipitating to realize the recovery of Fe element.
The positive electrode material mainly includes FePO4。
In this embodiment, the alkali solution may be strong alkali such as sodium hydroxide and potassium hydroxide, or weak alkali such as ammonia water.
Step S4, mixing and reacting the phosphate filtrate with the lithium hydroxide solution to generate lithium phosphate (Li)3PO4) Precipitation and alkali, thereby realizing the recovery of Li element and controlling the influence of P element on environment. In addition, because alkali is generated at the same time, the generated alkali can be used for preparing an alkali solution and reacting with other lithium ion battery positive electrode materials to be recovered to generate ferric hydroxide precipitates, so that the recovery of Fe elements of other lithium ion batteries to be recovered is realized. In other words, the base generated by the combined reaction of the phosphate filtrate and the lithium hydroxide solution also achieves a recycling economy.
According to the embodiment, the lithium ion battery can be safely disassembled, the battery components can be effectively separated, valuable metal elements in the waste lithium ion battery can be effectively recovered, and elements which are unfavorable for the environment can be controlled. The whole process flow is simple, efficient and environment-friendly, the experimental conditions are wide, the reliability is high, and the method has a good industrial application prospect.
It will be evident to those skilled in the art that the present application is not limited to the details of the foregoing illustrative embodiments, and that the present application may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the application being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (8)
1. A method for recycling a lithium ion battery, the method comprising:
removing the aluminum-plastic film shell of the charged lithium ion battery in an inert gas environment, and separating out a positive electrode material and a negative electrode material;
reacting the negative electrode material with water to obtain a lithium hydroxide solution, and separating graphite and a copper foil current collector;
reacting the positive electrode material with an alkali solution, and filtering to obtain ferric hydroxide precipitate; and
and mixing the phosphate filtrate with the lithium hydroxide solution for reaction to generate lithium phosphate precipitate and alkali.
2. The method for recovering a lithium ion battery according to claim 1, wherein: the method further comprises the following steps:
and charging the lithium ion battery to a voltage V1 by using a current I1 constant current, and then charging to a current I2 by using a voltage V2 constant voltage.
3. The method for recovering a lithium ion battery according to claim 2, wherein: i1 ═ 2A, V1 ═ V2 ═ 4V, and I2 ═ 0.02A.
4. The method for recovering a lithium ion battery according to claim 1, wherein: the water is industrial water, domestic water, deionized water, ultrapure water or high-temperature water vapor.
5. The method for recycling a lithium ion battery according to claim 4, wherein: the water contains ethanol.
6. The method for recycling a lithium ion battery according to claim 4, wherein: the water contains salt.
7. The method for recovering a lithium ion battery according to claim 1, wherein: the alkali solution is sodium hydroxide, potassium hydroxide or ammonia water.
8. The method for recovering a lithium ion battery according to claim 1, wherein: the inert gas is argon.
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| CN202011474696.3A CN112599879A (en) | 2020-12-14 | 2020-12-14 | Lithium ion battery recovery method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114725556A (en) * | 2022-04-06 | 2022-07-08 | 山东大学 | Method for recovering lithium from waste lithium ion battery |
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Application publication date: 20210402 |