CN113061726A - Method for safely and efficiently recycling lithium from waste batteries - Google Patents
Method for safely and efficiently recycling lithium from waste batteries Download PDFInfo
- Publication number
- CN113061726A CN113061726A CN202110274118.3A CN202110274118A CN113061726A CN 113061726 A CN113061726 A CN 113061726A CN 202110274118 A CN202110274118 A CN 202110274118A CN 113061726 A CN113061726 A CN 113061726A
- Authority
- CN
- China
- Prior art keywords
- lithium
- charging
- battery
- negative electrode
- solvent
- 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.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- 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
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- 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 provides a method for safely and efficiently recycling lithium from waste batteries, which comprises the following steps: the method comprises the steps of charging recycled waste batteries, disassembling the recycled waste batteries in a safe environment, sorting out negative plates, cleaning the negative plates by using a leaching solution, stripping graphite from a current collector after lithium in the negative plates reacts with a solvent, separating filtrate and filter residues, and reusing an enriched solution containing lithium as a chemical pre-lithiation reagent in the negative electrodes of the lithium ion batteries. According to the invention, the lithium element in the battery is safely and efficiently extracted by selecting the leaching solution, and the prepared lithium supplement solution with high added value is applied to the battery cathode again, so that the operation is simple and the safety is high.
Description
Technical Field
The invention designs a method for recycling lithium, and particularly relates to a method for recycling lithium from waste lithium batteries.
Background
The rapid development of industry and the growing wealth of modern society highlight the importance of developing sustainable and environmentally friendly economies. Energy crisis and environmental pollution become hot spots of research, wherein a great deal of research focuses on developing advanced electrochemical energy storage technology and electric automobiles, and lithium ion batteries are important components. In 2018, the loading capacity of lithium ion batteries exceeds 86% in the field of electrochemical energy storage, the inventory of global electric vehicles and newly registered electric vehicles respectively exceed 512 ten thousand and 197 ten thousand, and 2.53 hundred million electric vehicles on roads are predicted to be reached by 2030. This also means a huge consumption of lithium resources. The lithium ion battery has long cycle life, but still faces the problem of battery recovery, on one hand, the harm of heavy metals to the environment, and on the other hand, the limited resources require to recover the waste lithium ion battery. The estimate of the battery recycling industry is expected to reach $ 237.2 billion by 2030. Therefore, the method has high economic benefit and social benefit aiming at the recovery work of the waste lithium ion battery.
The existing lithium recovery method mainly comprises pyrometallurgy and hydrometallurgy, wherein the pyrometallurgy is simple to operate, but has high energy consumption and serious air pollution. The hydrometallurgical recovery has high purity, but uses a large amount of chemical reagents, usually comprises some strong acid and strong base, and has serious environmental pollution. Therefore, it is highly desirable and advantageous to develop a leaching solution that can safely and efficiently recover lithium and facilitate reuse.
CN108899601B discloses a method for recovering lithium and iron from lithium iron phosphate. Leaching the scrapped lithium iron phosphate with a strong acid solution to obtain iron and lithium, then converting the iron and lithium into lithium carbonate and iron phosphate, removing organic matters and carbon in the lithium carbonate and iron phosphate by calcining, and finally slurrying the lithium iron phosphate to prepare the battery-grade iron phosphate. The method uses a large amount of chemical reagents, including strong acid, and requires high-temperature calcination, so that the energy consumption is high and the environment is polluted.
CN110923453A discloses disassembling a battery in a charging state, separating a current collector with water, leaching and removing impurities by adjusting pH, and finally recovering lithium by an evaporative crystallization method, a precipitation method or a spray drying method. The method has serious potential safety hazard, the danger of directly treating the lithium-embedded cathode material by using water is high, various elements are designed in the impurity removal process, the operation is complex, and the obtained final product possibly contains more impurities.
Disclosure of Invention
The invention aims to solve the problem that a safe and efficient recovery method is designed, a high-value-added product enriched with lithium can be obtained through simple operation, and the method is beneficial to the next development and utilization.
A method for safely and efficiently recycling lithium from waste lithium batteries comprises the following steps:
1) the recycled waste batteries are disassembled after being charged, and negative plates are sorted out;
2) leaching and separating the negative plate by using a leaching solution;
3) separating the solid-liquid mixture obtained in the step 2) to obtain an enrichment solution of lithium;
4) applying the lithium enrichment solution to the lithium ion battery negative electrode for prelithiation;
the leaching solution is an organic solvent dissolved with substituted or unsubstituted polycyclic aromatic hydrocarbon, and the organic solvent is selected from one or more of ethers, esters and aromatic organic solvents.
In the invention, the charging process in the step 1) comprises one or more of constant current charging, constant voltage charging and constant current and constant voltage charging. In the invention, the constant current charging process comprises simple constant current charging and multi-section constant current charging, and the charging current range is 0.0.1-5C. Simple constant current charging is charging to a cutoff voltage at a specified current density. The multi-stage constant current charging comprises 2-6 constant current charging stages, the charging is carried out according to the preset charging current, and when the voltage of the battery reaches the preset voltage value, the charging automatically enters the next constant current stage until all the charging stages are finished. The current density of each constant current stage is less than that of the previous stage.
In the invention, the constant voltage charging is to apply constant voltage to charge the battery all the time in the charging process until the rated voltage of the battery is reached.
The constant-current constant-voltage charging process comprises three charging procedures, wherein the first stage selectively performs trickle charging on the battery according to the voltage condition of the battery, the battery enters a second stage constant-current charging stage after reaching a preset voltage, the voltage of the battery gradually rises at the moment, the battery is charged until the voltage reaches the rated voltage of the battery, the third stage constant-voltage charging stage is started, the voltage of the battery is kept constant, the charging current is reduced to be less than the preset charging cutoff current, the charging current is usually 5-15% of the constant-current charging current, and the charging process is finished.
The method combines the advantages of constant current charging and constant voltage charging, has the functions of repairing and activating the battery in the first stage, and simultaneously gives consideration to the charging speed and the charging capacity.
In the present invention, the dismantling in step 1) is performed in a safe environment, for example, with a relative humidity of less than 20% and less, preferably less than 10%.
In the present invention, the negative electrode in step 1) includes, but is not limited to, a lithium metal negative electrode, a carbon-based active material, and a silicon-based active material. The carbon active substance comprises but is not limited to one or more of natural graphite, artificial graphite, soft carbon, hard carbon and mesocarbon microbeads, and the silicon-based active substance comprises but is not limited to one or more of simple silicon, silicon alloy and silicon monoxide.
Preferably, in the invention, the negative plate is subjected to a plasma treatment step before the step 2), wherein the plasma treatment is to place the negative plate in a plasma reaction chamber and adopt Ar/N2The power of the gas source is 10-100W, the treatment time is 5-10min, the introduction amount of the working gas is 10-100sccm, and then the gas source is naturally cooled to the room temperature.
The inventor finds that the electrode plate after being charged and disassembled is subjected to plasma treatment, so that the electronic rearrangement of the lithium intercalation electrode plate can be promoted, and the migration rate of lithium ions and the extraction speed of lithium intercalation can be optimized. After the battery is safely disassembled in the constant-current and constant-voltage charging process, the battery is subjected to plasma treatment under the repairing and activating effects, so that the surface characteristics of the electrode plates are improved, and the electronic discharge is facilitated, so that the lithium leaching efficiency of subsequent leachate is improved.
In the invention, the leaching solution in the step 2) is an organic solvent in which polycyclic aromatic hydrocarbon is dissolved, wherein the polycyclic aromatic hydrocarbon has 10-30 carbon atoms and 2-4 rings; specifically selected from biphenyl, naphthalene, phenanthrene, anthracene, tetracene, pyrene and perylene. The polycyclic aromatic hydrocarbon is optionally substituted with 1 to 4 substituents including, but not limited to, alkyl (number of carbon atoms of 1 to 5, such as methyl, ethyl, propyl, butyl), hydroxyl, nitro, halogen (F, Cl, Br, I), amino, carboxyl, aldehyde, carbonyl, and the like.
The concentration of the polycyclic aromatic hydrocarbon in the leaching solution is 1-3mol/L, preferably 1-2 mol/L.
The invention preferably selects the polycyclic aromatic hydrocarbon substituted by halogen atoms and alkyl, on one hand, the compatibility of the polycyclic aromatic hydrocarbon with an organic solvent can be improved, on the other hand, the polycyclic aromatic hydrocarbon has an adjustable space structure and an electronic effect, and the potential difference between a leaching solution and a leached negative electrode is effectively adjusted, so that the leaching efficiency and the yield of lithium ions can be improved, and the subsequent development and utilization are facilitated. In addition, the halogen atom substituted polycyclic aromatic hydrocarbon used as the anode prelithiation reagent has promotion effect on stabilizing the interface.
In the present invention, the organic solvent is selected from one or more of ethers, esters, aromatics and other organic solvents, preferably ethers and esters, the ethers include tetrahydrofuran, ethylene glycol dimethyl ether, 1, 3-dioxolane, diethanol dimethyl ether, triethanol dimethyl ether, and tetraethanol dimethyl ether, the esters include ethylene carbonate, propylene carbonate, diethyl carbonate, and vinylene carbonate, and the aromatics include benzene, toluene and the like. More preferably, the organic solvent is a mixed organic solvent containing ether, for example, a mixed solvent composed of ether and ester or a mixed solvent composed of ether and aromatic.
The mixed solvent has good solubility to aromatic hydrocarbon, different solvents have different solvation degrees to lithium ions, the leaching efficiency can be accelerated by adjusting the proportion of the solvents, and meanwhile, the different solvents have different reaction activities, and the mixed solvent can form a more stable interface with an electrode material in subsequent application, so that the pre-lithiation material can be favorably exerted in a full battery. Among them, ethers have good solvation effect on lithium ions, and aromatic hydrocarbons are redox active in ether solvents, but have poor oxidation resistance, and have a narrow electrochemical window when used as lithium ion battery electrolyte. Ester solvents have high decomposition potential and good stability for commercial graphite cathodes, but aromatic hydrocarbons are redox-inert in ester solvents. Therefore, the mixed solvent is formed by compounding the ester solvent and the ether, so that the lithium in the cathode can be effectively extracted and recovered, and a stable interface can be formed in subsequent application. In addition, the aromatic solvent is favorable for enhancing the solubility of aromatic hydrocarbon and improving the extraction effect of lithium. Comprehensively considering the performances of all solvents, the mixed solvent is ethers and esters (ether: ester), or ethers and aromatics (ether: aromatic) according to the volume ratio of 1-7: 1, preferably an ether solvent and an ester solvent in a volume ratio of 1-5: 1.
In a preferred embodiment of the present invention, the leaching solution is a solution of biphenyl dissolved in an ether solvent and an ester solvent according to a volume ratio of 1-5: 1, wherein the concentration of biphenyl is 1-2 mol/L; more preferably, the ether solvent is at least one of ethylene glycol dimethyl ether, 1, 3-dioxolane, diethanol dimethyl ether, triethanol dimethyl ether and tetraethanol dimethyl ether; the ester solvent is at least one of ethylene carbonate and propylene carbonate.
In the invention, the leaching process in the step 2) is carried out under the protection of inert atmosphere, and the protection gas includes but is not limited to argon, nitrogen and the like, and argon is preferred. And a water content of 50ppm or less, preferably 1ppm or less, and an oxygen content of 50ppm or less, preferably 1ppm or less.
In the invention, the leaching temperature in the step 2) is 20-100 ℃, preferably 50-80 ℃, and the mass ratio of the electrode material to the solute to be leached is 1: 1.5-5, and the leaching time is 2-10 h.
In the invention, the general formula of the lithium enrichment solution in the step 3) is PAHx-·xLi+(1≤x≤10)。
According to the invention, through selection of the leaching solvent and regulation and control of reaction conditions in the leaching process, effective enrichment of lithium in the waste battery can be realized, and further recycling is realized.
In the invention, the lithium ion battery cathode in the step 4) includes, but is not limited to, a carbon-based active material, a silicon-based active material, a tin-based active material, a phosphorus-containing active material, a sulfur-containing active material, lithium titanate, and the like, wherein the carbon active material includes, but is not limited to, one or more of natural graphite, artificial graphite, soft carbon, hard carbon, and mesocarbon microbeads, and the silicon-based active material includes, but is not limited to, one or more of elemental silicon, a silicon alloy, and silica.
In the invention, the prelithiation method in the step 4) is characterized by comprising one or more of the following methods:
A) and (3) immersing the negative electrode material into the lithium enrichment solution in advance, and washing and drying after the reaction is completed to obtain the pre-lithiated negative electrode material.
B) And spraying or dropwise adding the lithium enrichment solution on the surface of the negative electrode, and washing and drying after the reaction is completed to obtain the pre-lithiated negative electrode material.
C) And (3) immersing the negative electrode material into the lithium enrichment solution in advance, and evaporating the solvent to dryness at a certain temperature to obtain the prelithiated negative electrode material.
Compared with the prior art, the invention has the advantages that:
the invention uses the leaching solution to safely and efficiently recover the lithium element, separates the lithium and other transition metal elements by an electrochemical method, efficiently and conveniently separates the lithium and other substances by utilizing the characteristics of good solvent safety and high extraction efficiency, and other components on the negative electrode can still be reused. The whole process avoids the use of high energy consumption and corrosive chemical reagents.
Compared with an aqueous solution or other small molecular solvents, the novel leaching solution is used, the activity of the novel leaching solution on lithium in the lithium intercalation graphite is regulated and controlled by the structure of a molecular design solute, the reaction rate with metal lithium can be controlled, and the lithium can be efficiently recovered under mild conditions.
The lithium-containing enrichment solution obtained by the invention can be directly applied to the lithium ion battery negative electrode prelithiation, the residual value of the recovered lithium is fully exerted, the battery is recovered and recycled to form a closed-loop industrial chain, and an intermediate treatment link is not needed.
And fourthly, the separation and post-treatment processes of the invention are simple to operate, high in safety, good in compatibility with the existing battery process, low in requirement on equipment and beneficial to realizing industrialization.
The novel leaching solution provided by the invention obtains a high-concentration lithium enrichment solution through selection and matching of solute and solvent, improves the utilization efficiency of lithium in the waste lithium battery, can be normally used or used in a gradient manner according to needs through simple lithium supplement, and has very high technical innovation and economic effect.
Sixth, the invention combines safe disassembly of charging with plasma treatment, optimizes the rearrangement of electrode structure, reduces the barrier of lithium ion migration, improves the extraction efficiency of lithium intercalation, is beneficial to the subsequent leaching efficiency, and obtains better recovery efficiency.
Drawings
FIG. 1 is a flow chart of a method for recycling lithium according to the present invention
FIG. 2 is a full cell charge-discharge curve assembled from pre-lithiated materials according to example 1 of the present invention
FIG. 3 is a graph of full cell cycle performance for pre-lithiated material assembly of example 1 of the present invention
Detailed Description
The present invention will be further described with reference to specific examples, but the present invention is not limited to the specific examples. All proportions in the examples of the present invention are mass ratios unless otherwise specified.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The electrochemical performance of the prelithiated negative electrodes prepared in the following examples were all tested as follows: and (3) mixing the prepared pre-lithiated negative electrode material, Super P and a polyacrylic acid binder in a mass ratio of 80: 10: 10, mixing the raw materials to prepare slurry, and uniformly coating the slurry on a copper foil current collector to obtain a working electrode; lithium iron phosphate, Super P and polyvinylidene fluoride binder are mixed according to a mass ratio of 80: 10: 10 to prepare a slurry, uniformly coating the slurry on an aluminum foil current collector to be used as a counter electrode, using polypropylene (purchased from Celgard corporation in the United states) as a diaphragm, using 1mol/L ternary electrolyte (1M LiPF6EC/DEC/DMC (volume ratio 1:1:1)) as an electrolyte, and assembling the slurry in a glove box to obtain a 2032 type button cell.
And (3) carrying out charge and discharge tests on the assembled battery on a LAND charge and discharge tester.
The calculation of the lithium extraction efficiency in the following embodiments can refer to GB/T23367.2-2009 and YS/T1006.2-2014, and the specific calculation method in the present case is as follows:
mLis the total mass of the diluted solution, x is the mass fraction of the metal element in the test sample, mSTo test the mass of the sample, mRFor the total mass of the sample recovered after leaching, mPIs the mass of the metal element in the selected battery material. Where x the metal content in the filtrates obtained under different conditions was quantitatively tested using a PerkinElmer Optima 8300ICP-OES system. The samples were diluted with 2% aqueous nitric acid and calibration curves were generated using at least 5 ICP standard solutions, resulting only from correlation coefficients greater than 0.999. Unless otherwise stated, the flow rate range of the gas atomizer was set to 0.45 to 0.75L min-1And the metal element uses 2 wavelengths in the axial mode: lithium (670.784nm (radial mode) and 610.362). The lithium extraction efficiency η of table 2 is reported below as the average of the extraction efficiencies of at least three replicate samples.
Example 1
(1) Charging the waste nickel cobalt lithium manganate battery by adopting a constant-current constant-voltage three-section charging mode, changing trickle charging to constant-current charging until the charging voltage reaches 3.5V, changing constant-current charging to 4.3V, changing constant-voltage charging again until the charging current density is reduced to 10 percent of the constant-current charging current density, keeping the voltage stable, and stopping charging;
(2) disassembling the waste lithium ion battery in a drying room with the relative humidity of 5%, taking out the disassembled negative plate, and cutting the negative plate into a proper size;
(3) and (3) carrying out plasma treatment on the negative plate: by using Ar/N2As a gas source, the power is 80W, the treatment time is 5min, the introduction amount of working gas is 30sccm, and then the gas is naturally cooled to room temperature;
(4) preparing a leaching solution, adding 15.4g of biphenyl and 100ml of diethylene glycol dimethyl ether solvent into a flask, and stirring until a clear and transparent solution is formed (the concentration of the biphenyl is 1 mol/L).
(5) Putting the negative pole pieces subjected to plasma treatment into a leaching solution in batches, wherein the leaching temperature is 60 ℃, and the solid-to-liquid ratio is 1: 3, leaching for 2 hours, after leaching, carrying out suction filtration on the solution, and separating to obtain a liquid phase and a solid phase;
(6) adding the silicon oxide/carbon composite material into the filtrate rich in lithium, and reacting for 2 hours at the reaction temperature of 60 ℃; cleaning for 3 times by using a diethylene glycol dimethyl ether solvent after the reaction is finished, and drying for later use;
(7) heating the pretreated silicon oxide/carbon composite material at 150 ℃ for 3h in an argon atmosphere, and sintering at 750 ℃ for 2h to obtain a final product after prelithiation;
(8) and (3) assembling the whole battery by using the pre-lithiated silicon monoxide/carbon composite material as a negative electrode and the lithium iron phosphate as a positive electrode, and performing charge and discharge tests. The results are shown in FIGS. 2 and 3.
Example 2
(1) Charging the waste lithium iron phosphate battery by adopting a constant-current constant-voltage three-section charging mode, changing trickle charging to constant-current charging until the charging voltage reaches 3.5V until the voltage reaches 4.2V, changing constant-voltage charging again until the charging current density is reduced to 10 percent of the constant-current charging current density, keeping the voltage stable, and stopping charging;
(2) disassembling the waste lithium ion battery in a drying room with the relative humidity of 5%, taking out the disassembled negative plate, and cutting the negative plate into a proper size;
(3) plasma treatment of a suitable negative plate: by using Ar/N2As a gas source, the power is 80W, the treatment time is 5min, the introduction amount of working gas is 50sccm, and then the gas is naturally cooled to the room temperature;
(4) preparing a leaching solution, adding 12.8g of naphthalene and 100ml of diethylene glycol dimethyl ether solvent into a flask, and stirring until a clear and transparent solution is formed;
(5) putting the negative pole pieces subjected to plasma treatment into a leaching solution in batches, wherein the leaching temperature is 60 ℃, and the solid-to-liquid ratio is 1: 3, leaching for 2 hours, after leaching, carrying out suction filtration on the solution, and separating to obtain a solid phase and a liquid phase rich in lithium;
(6) adding a hard carbon material into the filtrate rich in lithium, and reacting for 2 hours at the reaction temperature of 60 ℃; cleaning for 3 times by using a diethylene glycol dimethyl ether solvent after the reaction is finished, and drying for later use;
(7) and (3) assembling the whole battery by using the pre-lithiated hard carbon as a negative electrode and the lithium iron phosphate as a positive electrode, and performing charge and discharge tests.
Example 3
(1) Charging the waste lithium iron phosphate battery by adopting a constant-current constant-voltage three-section charging mode, changing trickle charging to constant-current charging until the charging voltage reaches 3.5V until the voltage reaches 4.2V, changing constant-voltage charging again until the charging current density is reduced to 10 percent of the constant-current charging current density, keeping the voltage stable, and stopping charging;
(2) disassembling the waste lithium ion battery in a drying room with the relative humidity of 5%, taking out the disassembled negative plate, and cutting the negative plate into a proper size;
(3) plasma treatment of a suitable negative plate: by using Ar/N2The power of the gas source is 100W, the treatment time is 5min, the introduction amount of working gas is 50sccm, and then the gas source is naturally cooled to the room temperature;
(4) preparing a leaching solution, adding 17.8g of phenanthrene and 100ml of diethylene glycol dimethyl ether solvent into a flask, and stirring until a clear and transparent solution is formed;
(5) putting the negative electrode slices subjected to plasma treatment into a leaching solution in batches, wherein the leaching temperature is 60 ℃, and the solid-to-liquid ratio is 1: 3, leaching for 2 hours, after leaching, carrying out suction filtration on the solution, and separating to obtain a liquid phase and a solid phase;
(6) adding the phosphorus/carbon composite material into the filtrate rich in lithium, and reacting for 2 hours at the reaction temperature of 60 ℃; cleaning for 3 times by using a diethylene glycol dimethyl ether solvent after the reaction is finished, and drying for later use;
(7) and (3) assembling the whole battery by using the pre-lithiated phosphorus/carbon composite material as a negative electrode and the lithium iron phosphate as a positive electrode, and performing charge and discharge tests.
Example 4
The rest was the same as in example 1 except that a leaching solution was prepared in step (4) with 20.2.g of pyrene as a solute.
Example 5
The same as in example 1 was repeated except that a leaching solution was prepared with 30.8g of biphenyl as a solute in step (4).
Example 6
The same as in example 1 was repeated except that a leaching solution was prepared in step (4) using 100ml of tetrahydrofuran as a solvent.
Example 7
The same as in example 1 was repeated except that a leaching solution was prepared in step (4) using 100ml of ethylene carbonate as a solvent.
Example 8
The same as in example 1 was repeated except that a leaching solution was prepared in step (4) using 100ml of a mixed solvent of diglyme and ethylene carbonate (volume ratio 1:1) as a solvent.
Example 9
The same procedure as in example 1 was repeated, except that the leaching solution was prepared in the step (4), and 15.4g of biphenyl and 100ml of a mixed solvent of diethylene glycol dimethyl ether and ethylene carbonate (volume ratio: 3: 1) were charged into a flask and stirred until a clear and transparent solution was formed.
Example 10
The same as example 1 was repeated except that in step (4), a novel leaching solution was prepared using 100ml of a mixed solvent of ethylene glycol dimethyl ether and ethylene carbonate (volume ratio 5: 1) as an organic solvent.
Example 11
The same as example 1 was repeated except that in step (4), a novel leaching solution was prepared using 100ml of a mixed solvent of diglyme and ethylene carbonate (volume ratio 7: 1) as a solvent.
Example 12
The same as example 1 was repeated except that in step (4), a novel leaching solution was prepared using 100ml of a mixed solvent of diglyme and ethylene carbonate (volume ratio 0.5: 1) as a solvent.
Example 13
The same procedure as in example 1 was repeated, except that the leaching solution was prepared in the step (4), and 15.4g of biphenyl and 100ml of a mixed solvent of diethylene glycol dimethyl ether and toluene (volume ratio: 2: 1) were charged into the flask, and stirred until a clear and transparent solution was formed.
Example 14
The same as in example 1 was repeated except that a leaching solution was prepared with 16.8g of 4-methylbiphenyl as a solute in step (4).
Example 15
The same as in example 1 was repeated except that a leaching solution was prepared with 18.8g of 4-chlorobiphenyl as a solute in step (4).
Example 16
The same as in example 1 was repeated except that 19.9g of 4-nitrobiphenyl was used as a solute to prepare a novel leaching solution in step (4).
Example 17
The same as example 1 except that 16.8g of 4-methylbiphenyl was used as a solute in step (4), and 100ml of a mixed solvent of diglyme and ethylene carbonate (volume ratio: 3: 1) was added to prepare a leaching solution.
Example 18
Otherwise, the negative electrode sheet was not plasma-treated, i.e., the plasma treatment step (3) was omitted, as in example 1.
In the examples included in the present invention, the physical properties of the polycyclic aromatic hydrocarbons used are shown in Table 1; the extraction effect of different leaching solutions on lithium in the lithium intercalated graphite is shown in table 2, and the extraction efficiency is calculated according to the extraction amount of lithium in the lithium intercalated graphite; different leach solutions were used as chemical prelithiation reagents and assembled full cell electrochemical performance tests are shown in table 3.
TABLE 1 physical Property parameter Table of polycyclic aromatic hydrocarbons
Table 2 table of the extraction efficiency of different leaching solutions for lithium
TABLE 3 COMPARATIVE TABLE FOR ELECTROCHEMICAL PERFORMANCE OF FULL CELL FOR DIFFERENT EXAMPLES
According to the embodiments, it can be seen that different polycyclic aromatic hydrocarbons have effects on extracting lithium from lithium intercalation graphite, and according to the oxidation-reduction potential of lithium by different polycyclic aromatic hydrocarbons, the extraction efficiency of lithium is increased along with the increase of the oxidation-reduction potential difference. Different solvents have different solvation effects on lithium in the reaction process, and have different extraction efficiencies on lithium. By combining the comprehensive comparison of the solubility of the polycyclic aromatic hydrocarbon in the solution and the extraction efficiency, we find that the biphenyl polycyclic aromatic hydrocarbon has a better application prospect in a mixed solvent containing ether in a proper proportion, the extraction efficiency of lithium is high, and as a prelithiation reagent, the first-turn coulomb efficiency of the assembled full-cell is high, and the cycle stability is better than that of a sample leached by using a single solvent. On the other hand, by designing the substituent groups of the polycyclic aromatic hydrocarbon, the potential difference between the leaching solution and the leached cathode can be effectively adjusted, and the leaching efficiency is further improved. By combining the two points, the polycyclic aromatic hydrocarbon modified by the functional group shows the best leaching efficiency in a mixed solvent system, and further, as a prelithiation reagent, the first-turn coulombic efficiency of the full battery is high, and the optimal embodiment 17 can reach 97.5%. In addition, the electrode sheet of example 18, which was not subjected to plasma treatment, had a slight decrease in lithium extraction efficiency and, in turn, had a slight decrease in electrochemical performance, but was still satisfactory.
In conclusion, the method provided by the invention is simple to operate, easy to regulate and control, and can safely and efficiently extract and recover lithium in the negative electrode to obtain the lithium-rich solution for prelithiation. The method solves the safety problem in the recovery process, is an important supplement for the development of the battery cathode, directly uses the recovered lithium for assembling the battery, has high cycle stability and has very high application prospect.
The above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the embodiments of the present invention, and those skilled in the art can easily make various changes or modifications according to the main concept and spirit of the present invention, so the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A method for safely and efficiently recycling lithium from waste batteries is characterized by comprising the following steps:
1) the recycled waste batteries are disassembled in a safe environment after being charged, and negative plates are sorted out;
2) leaching and separating the negative plate by using a leaching solution;
3) separating the solid-liquid mixture obtained in the step 2) to obtain an enrichment solution of lithium;
4) applying the lithium enrichment solution to the lithium ion battery negative electrode for prelithiation;
the leaching solution is an organic solvent dissolved with substituted or unsubstituted polycyclic aromatic hydrocarbon, and the organic solvent is selected from one or more of ethers, esters and aromatic organic solvents.
2. The method of claim 1, wherein the charging process in step 1) comprises one or more of constant current charging, constant voltage charging, and constant current and constant voltage charging; the constant-current constant-voltage charging process comprises three charging procedures, wherein the first stage selectively performs trickle charging on the battery according to the voltage condition of the battery, the battery enters a second stage constant-current charging stage after reaching a preset voltage, the voltage of the battery gradually rises at the moment, the battery is charged until the voltage reaches the rated voltage of the battery, the third stage constant-voltage charging stage is started, the voltage of the battery is kept constant, and the charging process is finished when the charging current is reduced to be smaller than the preset charging cutoff current.
3. The method of claim 1, wherein the safe environment of step 1) is a relative humidity of less than 20% and less, preferably less than 10%; the leaching process in the step 2) is carried out under the protection of inert atmosphere, and the protective gas comprises argon and nitrogen, preferably argon; and a water content of 50ppm or less, preferably 1ppm or less, and an oxygen content of 50ppm or less, preferably 1ppm or less.
4. The method of claim 1, wherein step 1) the negative electrode is selected from the group consisting of a lithium metal negative electrode, a carbon-based active material, a silicon-based active material; wherein the carbon active substance is selected from one or more of natural graphite, artificial graphite, soft carbon, hard carbon and mesocarbon microbeads, and the silicon-based active substance is selected from one or more of simple substance of silicon, silicon alloy and silicon monoxide.
5. The method according to claim 1, wherein step 2) is preceded by a step of performing plasma treatment on the disassembled negative electrode plate, wherein the plasma treatment is to place the negative electrode plate in a plasma reaction chamber and adopt Ar/N2The power of the gas source is 10-100W, the treatment time is 5-10min, the introduction amount of the working gas is 10-100sccm, and then the gas source is naturally cooled to the room temperature.
6. The method of claim 1, wherein the polycyclic aromatic hydrocarbon has 10 to 30 carbon atoms and 2 to 4 rings, and is selected from biphenyl, naphthalene, phenanthrene, anthracene, tetracene, pyrene, perylene.
7. The method of claim 6, wherein the polycyclic aromatic hydrocarbon is optionally substituted with 1 to 4 substituents comprising alkyl groups, hydroxyl groups, nitro groups, halogen atoms, amino groups, carboxyl groups, aldehyde groups, carbonyl groups.
8. The method of claim 7, wherein the concentration of polycyclic aromatic hydrocarbons in the leach solution is between 1 and 3 mol/L.
9. The method according to claim 1, wherein the organic solvent is a mixed solvent of ethers and esters, or ethers and aromatics in a volume ratio of 1-7: 1, preferably an ether solvent and an ester solvent in a volume ratio of 1-5: 1, a mixed solvent; the ether solvent is selected from tetrahydrofuran, ethylene glycol dimethyl ether, 1, 3-dioxolane, diethanol dimethyl ether, triethanol dimethyl ether and tetraethanol dimethyl ether, and the ester solvent is selected from ethylene carbonate, propylene carbonate, diethyl carbonate and vinylene carbonate; the aromatic solvent is selected from benzene and toluene.
10. The method according to claim 1, wherein the leaching temperature in step 2) is 20-100 ℃, preferably 50-80 ℃, and the mass ratio of electrode material to solute to be leached is 1: 1.5-5, and the leaching time is 2-10 h; the lithium ion battery cathode in the step 4) comprises a carbon-based active substance, a silicon-based active substance, a tin-based active substance, a phosphorus-containing active substance, a sulfur-containing active substance and lithium titanate, wherein the carbon-based active substance comprises one or more of natural graphite, artificial graphite, soft carbon, hard carbon and mesocarbon microbeads, and the silicon-based active substance comprises one or more of a silicon simple substance, a silicon alloy and silicon monoxide;
the prelithiation process of step 4), comprising one or more of the following processes:
A) and (3) immersing the negative electrode material into the lithium enrichment solution in advance, and washing and drying after the reaction is completed to obtain the pre-lithiated negative electrode material.
B) And spraying or dropwise adding the lithium enrichment solution on the surface of the negative electrode, and washing and drying after the reaction is completed to obtain the pre-lithiated negative electrode material.
C) And (3) immersing the negative electrode material into the lithium enrichment solution in advance, and evaporating the solvent to dryness at a certain temperature to obtain the prelithiated negative electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110274118.3A CN113061726B (en) | 2021-03-15 | 2021-03-15 | Method for safely and efficiently recycling lithium from waste batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110274118.3A CN113061726B (en) | 2021-03-15 | 2021-03-15 | Method for safely and efficiently recycling lithium from waste batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113061726A true CN113061726A (en) | 2021-07-02 |
| CN113061726B CN113061726B (en) | 2021-11-23 |
Family
ID=76560558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110274118.3A Active CN113061726B (en) | 2021-03-15 | 2021-03-15 | Method for safely and efficiently recycling lithium from waste batteries |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113061726B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113594419A (en) * | 2021-07-28 | 2021-11-02 | 湖南立方新能源科技有限责任公司 | Lithium supplementing method for negative electrode and application thereof |
| CN113846235A (en) * | 2021-11-16 | 2021-12-28 | 中国科学院化学研究所 | Closed-loop recycling method for lithium in lithium ion battery |
| CN113871733A (en) * | 2021-08-31 | 2021-12-31 | 湖南立方新能源科技有限责任公司 | Lithium supplementing method for diaphragm and application thereof |
| CN113904018A (en) * | 2021-10-13 | 2022-01-07 | 广东邦普循环科技有限公司 | Method for preparing active negative electrode material by recovering battery powder leaching residue |
| CN114447465A (en) * | 2022-01-14 | 2022-05-06 | 清华大学深圳国际研究生院 | Method and material for synergistically regenerating anode material and cathode material of lithium ion battery and application of material |
| CN114890868A (en) * | 2022-06-15 | 2022-08-12 | 清华大学深圳国际研究生院 | Method for recovering lithium ion battery negative electrode material and organic lithium compound |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150014890A1 (en) * | 2013-07-10 | 2015-01-15 | GM Global Technology Operations LLC | Surface coating method and method for improving electrochemical performance of an electrode for a lithium based battery |
| KR101621312B1 (en) * | 2015-10-15 | 2016-05-16 | 이치헌 | Method Of Recycling Resource for lithium ion secondary battery |
| CN110120496A (en) * | 2018-02-05 | 2019-08-13 | 武汉大学 | A kind of negative electrode of lithium ion battery and its prelithiation methods and applications |
| CN110923453A (en) * | 2019-11-29 | 2020-03-27 | 中南大学 | Method for recovering lithium from waste lithium ion battery |
| CN111128567A (en) * | 2019-12-23 | 2020-05-08 | 中国电子科技集团公司第十八研究所 | Preparation method of organic prelithiation material |
| CN111224187A (en) * | 2019-11-04 | 2020-06-02 | 中国科学院化学研究所 | Method for directly repairing and regenerating waste lithium iron phosphate battery positive electrode material |
| CN112219296A (en) * | 2018-01-19 | 2021-01-12 | 安普瑞斯股份有限公司 | Stabilized prelithiated silica particles for lithium ion battery anodes |
| CN112490394A (en) * | 2020-11-30 | 2021-03-12 | 武汉大学 | Chemical prelithiation method for graphite electrode of lithium ion battery |
-
2021
- 2021-03-15 CN CN202110274118.3A patent/CN113061726B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150014890A1 (en) * | 2013-07-10 | 2015-01-15 | GM Global Technology Operations LLC | Surface coating method and method for improving electrochemical performance of an electrode for a lithium based battery |
| KR101621312B1 (en) * | 2015-10-15 | 2016-05-16 | 이치헌 | Method Of Recycling Resource for lithium ion secondary battery |
| CN112219296A (en) * | 2018-01-19 | 2021-01-12 | 安普瑞斯股份有限公司 | Stabilized prelithiated silica particles for lithium ion battery anodes |
| CN110120496A (en) * | 2018-02-05 | 2019-08-13 | 武汉大学 | A kind of negative electrode of lithium ion battery and its prelithiation methods and applications |
| CN111224187A (en) * | 2019-11-04 | 2020-06-02 | 中国科学院化学研究所 | Method for directly repairing and regenerating waste lithium iron phosphate battery positive electrode material |
| CN110923453A (en) * | 2019-11-29 | 2020-03-27 | 中南大学 | Method for recovering lithium from waste lithium ion battery |
| CN111128567A (en) * | 2019-12-23 | 2020-05-08 | 中国电子科技集团公司第十八研究所 | Preparation method of organic prelithiation material |
| CN112490394A (en) * | 2020-11-30 | 2021-03-12 | 武汉大学 | Chemical prelithiation method for graphite electrode of lithium ion battery |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113594419A (en) * | 2021-07-28 | 2021-11-02 | 湖南立方新能源科技有限责任公司 | Lithium supplementing method for negative electrode and application thereof |
| CN113871733A (en) * | 2021-08-31 | 2021-12-31 | 湖南立方新能源科技有限责任公司 | Lithium supplementing method for diaphragm and application thereof |
| CN113871733B (en) * | 2021-08-31 | 2023-10-31 | 湖南立方新能源科技有限责任公司 | Lithium supplementing method of diaphragm and application of lithium supplementing method |
| CN113904018A (en) * | 2021-10-13 | 2022-01-07 | 广东邦普循环科技有限公司 | Method for preparing active negative electrode material by recovering battery powder leaching residue |
| CN113846235A (en) * | 2021-11-16 | 2021-12-28 | 中国科学院化学研究所 | Closed-loop recycling method for lithium in lithium ion battery |
| CN113846235B (en) * | 2021-11-16 | 2022-10-21 | 中国科学院化学研究所 | Closed-loop recycling method for lithium in lithium ion battery |
| CN114447465A (en) * | 2022-01-14 | 2022-05-06 | 清华大学深圳国际研究生院 | Method and material for synergistically regenerating anode material and cathode material of lithium ion battery and application of material |
| CN114890868A (en) * | 2022-06-15 | 2022-08-12 | 清华大学深圳国际研究生院 | Method for recovering lithium ion battery negative electrode material and organic lithium compound |
| CN114890868B (en) * | 2022-06-15 | 2024-04-19 | 清华大学深圳国际研究生院 | Method for recycling lithium ion battery anode material and organic lithium compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113061726B (en) | 2021-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113061726B (en) | Method for safely and efficiently recycling lithium from waste batteries | |
| Arshad et al. | A comprehensive review of the advancement in recycling the anode and electrolyte from spent lithium ion batteries | |
| Raj et al. | Recycling of cathode material from spent lithium-ion batteries: Challenges and future perspectives | |
| Li et al. | The recycling of spent lithium-ion batteries: a review of current processes and technologies | |
| Xiao et al. | Recycling metals from lithium ion battery by mechanical separation and vacuum metallurgy | |
| Xu et al. | A review of processes and technologies for the recycling of lithium-ion secondary batteries | |
| CN109449523B (en) | Comprehensive recovery method for waste lithium ion battery | |
| Chen et al. | Leaching of cathode materials from spent lithium-ion batteries by using a mixture of ascorbic acid and HNO3 | |
| Li et al. | Ascorbic-acid-assisted recovery of cobalt and lithium from spent Li-ion batteries | |
| Zheng et al. | Leaching procedure and kinetic studies of cobalt in cathode materials from spent lithium ion batteries using organic citric acid as leachant | |
| CN103915661B (en) | A kind of direct recovery the method repairing anode material for lithium-ion batteries | |
| CN102751548B (en) | Method for recovering and preparing lithium iron phosphate from waste lithium iron phosphate battery | |
| Yang et al. | Recovery and regeneration of LiFePO 4 from spent lithium-ion batteries via a novel pretreatment process | |
| CN108808150B (en) | Method for comprehensively recycling waste ternary electrode material | |
| CN104810566B (en) | A kind of waste lithium iron phosphate electrokinetic cell green reclaim processing method | |
| JP2000173677A (en) | Lithium battery processing method for recycling constituent material | |
| CN112939096A (en) | Direct repairing method for ternary cathode material of waste lithium ion battery | |
| CN104183888A (en) | Green method for recovery and disposal of waste lithium iron phosphate power battery | |
| CN113846235B (en) | Closed-loop recycling method for lithium in lithium ion battery | |
| CN101030663A (en) | Method for recovering and regenerating refused battery critical material | |
| KR20210145454A (en) | Reuse method of active material of positive electrode scrap | |
| Qin et al. | Recovery and reuse of spent LiFePO4 batteries | |
| Natarajan et al. | Recycling of spent graphite and copper current collector for lithium-ion and sodium-ion batteries | |
| CN103367839B (en) | A kind of method reclaiming separation anode pole piece from waste and old lithium ion battery | |
| US20210242514A1 (en) | Systems and methods for recycling electrodes |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |