CN113437378A - Method for recycling and reusing anode and cathode of waste battery - Google Patents
Method for recycling and reusing anode and cathode of waste battery Download PDFInfo
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- CN113437378A CN113437378A CN202110675254.3A CN202110675254A CN113437378A CN 113437378 A CN113437378 A CN 113437378A CN 202110675254 A CN202110675254 A CN 202110675254A CN 113437378 A CN113437378 A CN 113437378A
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for recycling and reusing anodes and cathodes of waste batteries with different electric quantities. The method comprises the following steps: disassembling a waste lithium iron phosphate battery, collecting a lithium-removed positive electrode and a lithium-inserted graphite negative electrode, then placing the lithium-inserted graphite in deionized water, ultrasonically recovering lithium and graphite, and finally, synthesizing a positive electrode material for the lithium ion battery again by taking a recovered lithium product as a lithium source and the lithium-removed positive electrode; the waste graphite after lithium removal and lithium extraction is used as a lithium ion battery cathode material for recycling or is used as a sodium ion battery cathode material after ball milling. The method provided by the invention is beneficial to promoting the recovery of the waste lithium battery with high efficiency and low cost, and has certain practical application value.
Description
Technical Field
The invention belongs to the field of recycling of waste lithium batteries, and particularly relates to a method for recycling and reusing positive and negative electrodes of waste batteries.
Background
Lithium batteries are used as energy storage and conversion devices and play an important role in the field of new energy. In recent years, with the concern of ecological environment, many countries have made many active policies in the application and recycling of lithium batteries, so that the development of lithium batteries is more and more emphasized in the present society. Since the lithium ion battery was first commercialized by sony corporation in the last 90 th century, the lithium ion battery has the advantages of high energy storage density, no memory effect, low self-discharge rate, long cycle life, small volume, less pollution and the like, the industry is rapidly developed and is widely applied, for example, in the fields of smart phones, notebook computers, digital cameras, electric vehicles, aerospace and the like, if the lithium ion battery industry is continuously upgraded, higher industrial standards and requirements are inevitably provided for the production and recovery fields of the lithium ion battery, since the new energy vehicles are vigorously popularized in the state of 2013, the trend of using the new energy vehicles in China is increased every year, the production demand of the lithium ion battery is rapidly increased, and the problem of large-scale recovery of the lithium ion battery is more prominent. The average service life of automobile lithium batteries in the market is 5-7 years, and is estimated to exceed 78 ten thousand tons in 2025 years. In the waste lithium battery, the mass fractions of Co, Li and Ni are respectively 5.0-15.0%, 2.0-7.0% and 0.5-2.0%, and metal elements such as Al, Cu and Fe are also contained; from the main component value ratio, the anode material and the cathode material account for about 33% and 10%, and the electrolyte and the diaphragm account for about 12% and 30%, respectively. Therefore, recycling valuable metals contained in the waste lithium batteries is undoubtedly an effective way for solving the current domestic resource shortage.
In order to solve the problem of recycling waste batteries, valuable metals are recovered from waste lithium batteries by various physical and chemical methods, mainly including hydrometallurgy (using a large amount of acid or alkali or organic matter), pyrometallurgy and a combination of the two methods. In the conventional recovery method, various valuable elements are leached by acid, and the lithium element can be finally extracted due to the physical and chemical characteristics of the lithium element, so that the lithium element is greatly lost in the process, and impurities in the filtrate cause low purity of the recovered lithium compound. And recovery of valuable metal elements (e.g. Co andni) has received relatively little attention to selective recovery of Li than has been paid to the progress made. The method for recovering lithium from the negative electrode material of the lithium battery [ P ] is established in Zhang Yunhe, a way of recovering lithium in the negative electrode material of the lithium battery [ P ] in experiments, wherein graphite of the negative electrode of the lithium battery is used as an anode, lithium metal is used as a cathode, lithium hexafluorophosphate (the concentration is 1mol/L) is used as electrolyte to form a three-electrode system]Hubei province: CN107069133B,2019-10-25), it can be seen that the recovery of lithium element from waste graphite of lithium battery has certain feasibility. On the other hand, since Li raw material (e.g. Li)2CO3) Is short of supply and costs are increased, and thus recycling of the waste lithium batteries is an effective method for solving the problem. Besides selective recovery of lithium, in the conventional recovery approach, the recovery of the graphite cathode is concerned a little, the conventional treatment modes such as landfill and incineration cause serious resource waste, and volatilization of organic compounds containing fluorine, phosphorus and the like in the graphite cathode material also harms the environment. Although flake graphite used for a negative electrode of a lithium battery is naturally abundant and relatively inexpensive, flake graphite is an irrenewable resource, and it has been considered as one of the most important strategic materials with the large use of graphite in various fields, such as lithium batteries, metallurgy, and other energy storage systems. Therefore, the effective recovery of the waste lithium battery is crucial to the sustainable development by integrating the factors of resource recycling, environmental protection and the like.
Disclosure of Invention
Aiming at the problems of complex operation, high pollution, harsh recovery conditions and the like of the existing recovery process, the invention provides a method for recovering and recycling the anode and the cathode of the waste battery on the basis of overcoming the defects of the prior art.
According to the method, clean and environment-friendly deionized water is adopted, lithium elements in the lithium-intercalated graphite are extracted selectively by ultrasonic at room temperature, the extraction rate reaches 99.1%, and the extracted lithium is used as a lithium source and a lithium-removing anode material to synthesize a lithium iron phosphate anode material again; meanwhile, the graphite after lithium extraction is reused in a lithium ion battery or used as a negative electrode material of a sodium ion battery after ball milling, so that the high-efficiency recovery and reutilization of the waste lithium battery are realized.
The invention aims to provide a method for recovering lithium, graphite and a lithium removal positive electrode material from waste batteries with different electric quantities.
The second purpose of the invention is to provide an efficient and environment-friendly water leaching method for recovering lithium and graphite materials from lithium-intercalated graphite.
The invention has simple process, can realize large-scale production, provides reference for recycling and reusing of waste batteries, and can generate higher economic benefit and social benefit.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a method for recycling and reusing anodes and cathodes of waste batteries, which comprises the following steps:
(1) disassembling the waste battery to obtain a lithium-removed positive electrode and a lithium-intercalated graphite negative electrode, then placing the lithium-intercalated graphite negative electrode in a reaction container, and then introducing water vapor and protective gas for carrying out co-heat treatment to obtain heat-treated lithium-rich graphite;
(2) soaking the lithium-rich graphite subjected to heat treatment in the step (1) in water, performing ultrasonic treatment, filtering and separating filtrate and filter residue, concentrating the filtrate, and drying to obtain a lithium source, wherein the filter residue is graphite subjected to lithium extraction;
(3) uniformly mixing the lithium source obtained in the step (2), the lithium-removing anode obtained in the step (1) and a carbon source to obtain a mixture, and heating for calcination treatment to obtain a lithium iron phosphate anode;
(4) and (3) using the graphite subjected to lithium removal in the step (2) for preparing a lithium ion battery or preparing a negative electrode material of a sodium ion battery after ball milling treatment.
The waste battery in the step (1) can contain different electric quantities. The main component of the anode material of the waste battery is lithium iron phosphate, and the main component of the cathode material of the waste battery is graphite. The waste battery packaging form comprises but is not limited to one of a hard shell lithium battery, a soft package lithium battery and a box type lithium battery.
Preferably, the waste battery in the step (1) is a full-capacity soft-package waste lithium battery.
Further, in the step (1), when the waste batteries are disassembled, the relative humidity of air is less than 10%.
Further, the protective gas in the step (1) is one of argon and nitrogen; the water vapor is generated by the water passing through a peristaltic pump and then through a steam generator.
Preferably, the protective gas in step (1) is argon.
Further, the water replenishing rate of the peristaltic pump is 0.02-0.5 mL/min.
Preferably, the water replenishing rate of the peristaltic pump is 0.05 mL/min.
Further, the temperature of the co-heat treatment in the step (1) is 400-.
Preferably, the temperature of the co-heat treatment in the step (1) is 800 ℃, and the time of the co-heat treatment is 2 h.
Preferably, the reaction vessel in step (1) is a tube furnace.
Further, the mass-to-volume ratio of the lithium-rich graphite subjected to heat treatment in the step (2) to water is 1:20-1:80 g/mL; the power of ultrasonic treatment is 80-120W, and the time of ultrasonic treatment is 40-70 min. The temperature of the sonication was room temperature.
Preferably, the water in step (2) is one of mineralized water, purified water, hard water and soft water.
Further preferably, the water in step (2) is deionized water.
Preferably, the mass-to-volume ratio of the lithium-rich graphite to water after the heat treatment in the step (2) is 1:50 g/mL.
Preferably, the power of the ultrasonic treatment is 100W, and the time of the ultrasonic treatment is 60 min.
In the step (2), the graphite after lithium extraction can be directly reused as a lithium ion battery cathode material or used as a sodium ion battery cathode after ball milling treatment.
Preferably, the drying manner in the step (2) is one of drying under normal pressure, drying under reduced pressure, spray drying, boiling drying and freeze drying.
Further preferably, the drying mode in the step (2) is freeze drying.
Further, the carbon source in the step (3) is more than one of glucose, sucrose and citric acid; the mass ratio of the lithium source to the lithium removal anode is 1:2-1: 4; the mass ratio of the delithiation anode to the carbon source is 1:1.8-1: 3.
Preferably, the carbon source in step (3) is glucose.
Preferably, the mass ratio of the lithium source to the lithium-removing positive electrode in the step (3) is 1:3, and the mass ratio of the lithium-removing positive electrode to the carbon source is 1: 2.4.
Further, the calcination treatment of step (3) comprises: pre-burning for 2.5-3.5h at the temperature of 280-320 ℃ and then calcining for 9-11h at the temperature of 700-800 ℃.
Preferably, the calcination treatment of step (3) comprises: presintering at 300 deg.c for 3 hr, and calcining at 750 deg.c for 10 hr.
Uniformly mixing the lithium leached in the step (3) as a lithium source, the delithiated positive electrode as an iron source and a phosphorus source with an external carbon source, and then calcining to synthesize the lithium iron phosphate positive electrode material for the lithium ion battery.
Further, the rotation speed of the ball milling treatment in the step (4) is 300-.
Preferably, the rotation speed of the ball milling treatment in the step (4) is 400rpm, and the time of the ball milling treatment is 48 h.
Preferably, the medium used in the ball milling treatment in step (4) is one or more of stainless steel balls, zirconium balls, agate balls, forged steel balls, cast iron balls, ceramic balls, manganese cast iron balls, ceramic balls and gravels.
Further preferably, the medium used in the ball milling treatment in the step (4) is stainless steel balls.
Preferably, the ball-milling treatment has a ball-to-feed ratio of 100: 1.
The invention provides a method for recycling and reusing anodes and cathodes of waste batteries with different electric quantities, wherein the anodes and cathodes of the waste batteries are composed of Li embedded lithium graphite obtained after the waste batteries are disassembledxC6Belongs to a graphite interlayer compound, wherein the lithium content is increased along with the increase of the electric quantity of a waste batteryThe graphite is different from the conventional graphite or the graphite disassembled from the waste battery after complete discharge treatment. The inventor finds that the SEI film on the surfaces of the binder and the graphite is easy to generate amorphous carbon at high temperature through a great deal of research, so that the weak oxidant water is added in the heat treatment process, and the weak oxidant water can be used for removing the amorphous carbon or can react with the surface of the waste graphite to optimize the crystallinity of the graphite, so that the performance of the graphite after being reused in the negative electrode of the lithium ion battery is better. Secondly, when the unstable carbon is taken away by the water reaction, the enrichment of lithium element is also facilitated.
In the preparation method provided by the invention, the abundance of lithium in the lithium-intercalated graphite and the recovery rate of graphite are higher.
The invention provides a method for recycling and reusing anodes and cathodes of waste batteries with different electric quantities, which is characterized in that four essential sources of lithium obtained by extracting lithium-intercalated graphite are provided, wherein one essential source is lithium remained in electrolyte; secondly, lithium irreversibly inserted into the graphite layer; thirdly, organic/inorganic lithium in the SEI film; and fourthly, lithium inserted into the graphite layer, wherein the source of the extracted lithium is mainly lithium inserted into the graphite layer.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the method can give consideration to the recovery and reutilization of lithium element, graphite and anode materials, and the method for extracting lithium by adopting the lithium-intercalated graphite can avoid complicated acid leaching and impurity removal processes, thereby overcoming the defects of high lithium recovery difficulty, large pollution, low recovery rate and low purity in the traditional process.
(2) The heat treatment method provided by the invention can improve the abundance of extractable lithium element in graphite, the residual rate of the treated lithium-rich graphite is 59.5%, the content of the lithium element in the treated lithium-rich graphite is 11% by ICP test, and the extraction efficiency of deionized water reaches 99.1%; the filtrate is directly concentrated and dried without purification, and tested for Li by ICP2CO3The mass fraction of (A) is 97%; the recycled graphite is directly used for the negative electrode of the lithium ion battery, the reversible capacity of 323mAh/g and the first coulombic efficiency of 72 percent can be obtained under 0.1C (37.2mA/g), the reversible capacity close to 300mAh/g can be obtained under 1C, and the performance is close to or superior to that of brand-new commercial graphite;when the ball-milled graphite is used for a sodium ion battery cathode, the first coulombic efficiency reaches 80.1%, and the reversible capacity of 203mAh/g can be obtained under the high multiplying power of 1000 mA/g; the lithium iron phosphate anode material prepared by the lithium source and the lithium-removing anode provided by the invention has high purity and crystallinity, and the reversible capacity under 0.1C can reach 155mAh g-1。
Drawings
FIG. 1 is a flow chart of a process for recycling and reusing waste lithium batteries according to the present invention;
FIG. 2a is a scanning electron microscope image of a lithium-intercalated graphite negative electrode obtained by disassembling a waste lithium battery in example 1;
FIG. 2b is a scanning electron micrograph of lithium-rich graphite after water vapor heat treatment of example 1;
FIG. 2c is a scanning electron micrograph of the graphite after extraction of lithium from the lithium-rich graphite water of example 1;
FIG. 3 is a morphology chart of ball-milled waste graphite prepared by ball milling waste graphite after lithium extraction in example 1;
FIG. 4a is an XRD (X-ray diffraction) spectrum before and after lithium extraction of lithium-intercalated graphite in example 1;
FIG. 4b is a comparative XRD pattern of recovered lithium carbonate from lithium extraction with water and standard lithium carbonate card;
FIG. 5a is a constant current charge/discharge diagram of a second cycle of the lithium ion battery with graphite extracted in example 1;
FIG. 5b is a graph showing the rate capability of the lithium ion battery made of the waste graphite after lithium extraction in example 1;
FIG. 6 is a graph of the rate capability of the ball-milled graphite sodium-ion battery obtained in example 1;
fig. 7 is an XRD spectrum of the lithium iron phosphate cathode material and the standard card newly prepared in example 1;
fig. 8a is a constant current charge and discharge diagram of a lithium ion battery of the lithium iron phosphate cathode material newly prepared in example 1;
fig. 8b is a rate capability diagram of the lithium ion battery of the lithium iron phosphate cathode material newly prepared in example 1.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
A method for recycling and reusing anodes and cathodes of waste batteries with different electric quantities comprises the following steps:
(1) disassembling waste lithium batteries with full electric quantity to obtain negative lithium-embedded graphite and a lithium-removed positive electrode material, putting 2g of the negative electrode of the lithium-embedded graphite into a tubular furnace, introducing water and argon for co-heat treatment, wherein the flow rate of the argon is 50mL/min, the water replenishing rate of a peristaltic pump is 0.05mL/min, heating the two materials by a steam generator, introducing the heated materials into the tubular furnace together, heating to 800 ℃ at the rate of 20 ℃/min, and keeping the temperature for 2 hours to obtain the lithium-rich graphite after heat treatment, wherein the residual rate of the graphite is 59.5%.
(2) Adding 1g of the heat-treated lithium-rich graphite into 50mL of deionized water, carrying out ultrasonic treatment for 60min at 100W by using ultrasonic waves, filtering and washing to obtain filtrate and a filter cake (waste graphite filter cake), carrying out freeze drying on the filtrate to obtain a white lithium compound solid, and carrying out vacuum drying on the filter cake to obtain the recovered graphite. The content of lithium element in the lithium-rich graphite (recovered graphite) in ICP test is 11.0%, and the extraction efficiency of deionized water reaches 99.1%.
(3) Mixing 1g of recovered graphite with 100g of stainless steel balls (the diameter of each stainless steel ball is 5mm), introducing argon, putting the mixture into a ball mill, carrying out ball milling for 48 hours at the speed of 500rpm, carrying out Soxhlet extraction, washing, and freeze-drying for later use to obtain the ball-milled graphite.
(4) And (2) placing 3g of the lithium-removing anode material in the step (1) in a tubular furnace, introducing argon at the flow rate of 50mL/min as protective atmosphere, heating to 500 ℃ at the heating rate of 3 ℃/min, and preserving heat for 2h to obtain the pretreated lithium-embedded anode. And then, taking the pretreated delithiated positive electrode as an iron source and a phosphorus source, taking a lithium compound as a lithium source in the step (2), and taking glucose as an external carbon source, wherein the mass ratio of the lithium source to the delithiated positive electrode is 1:3, the mass ratio of the lithium-removing anode to the carbon source is 1:2.4, mixing the three raw materials, putting 3g of the mixture into a tube furnace, introducing argon at a flow rate of 50mL/min as a protective atmosphere, heating at a heating rate of 3 ℃/min to 300 ℃, and preserving heat and presintering for 3 hours. And finally, grinding the pre-sintered material, performing dry pressing, putting the material in a tubular furnace again, introducing argon at the flow rate of 50mL/min as protective atmosphere, heating at the heating rate of 3 ℃/min to 750 ℃, and calcining for 10 hours at high temperature to prepare the lithium iron phosphate cathode material.
The ball-milled graphite sample provided in example 1 was applied to a sodium ion battery negative electrode material to detect its energy storage effect. The application method comprises the following steps:
A. grinding ball-milled graphite, acetylene black and a binder (PVDF) for 30min and uniformly mixing according to the mass ratio of 9:0.5:0.5, adding 0.7mL of nitrogen methyl pyrrolidone serving as a solvent, continuously grinding for 10min and uniformly mixing to obtain electrode slurry, coating the electrode slurry on a copper foil, and performing vacuum drying at 90 ℃ to obtain a battery negative plate for later use.
B. And assembling the battery negative plate, a positive plate, a sodium plate, a glass fiber diaphragm, 1mol/L sodium bis (fluorosulfonyl) imide (the solvent is triethylene glycol dimethyl ether), a gasket, an elastic sheet and a negative plate in an Ar atmosphere glove box to form a sodium ion half battery, and testing the battery by adopting a blue battery charge-discharge testing system.
In addition, the ball-milled graphite obtained in the step (3) and the lithium iron phosphate material obtained in the step (4) can be reused for assembling the lithium ion half-cell, the preparation and assembly methods of the lithium ion cell pole piece related by the invention adopt conventional known methods, which are not described herein again, and the mass ratio of the materials of the positive pole piece and the negative pole piece of the lithium ion cell in the embodiment of the invention is 9:0.5: 0.5.
Effect verification
By adopting the process flow (figure 1) of the invention, the lithium content of the lithium-removed anode disassembled according to the embodiment 1 is found to be reduced to 0.12% through ICP (inductively coupled plasma) test, and the lithium content of the lithium-inserted anode is increased to 6.30%, which indicates that almost all lithium in the anode in the waste battery is removed and inserted into the graphite layer of the anode. FIG. 2a is a schematic diagram of a negative electrode of lithium-intercalated graphite obtained by disassembling a waste lithium battery, the surface of which is attached with a plurality of amorphous compounds; fig. 2b shows that after heat treatment, the amorphous compound on the surface of the lithium-intercalated graphite disappears, the graphite surface becomes smooth and corroded, and fig. 2c shows that the morphology structure of the waste graphite after lithium extraction does not change significantly. FIG. 3 shows that after lithium extraction, waste graphite is subjected to ball milling in an argon atmosphere to become graphene nanosheets, and the graphene nanosheets have high surface energy and are agglomerated. The XRD pattern in fig. 4a shows that the lithium-intercalated graphite impurity peak disappears after water extraction of lithium, indicating that all lithium in the lithium-rich graphite has been extracted, and that the filtrate after drying has a composition mainly of lithium carbonate, high crystallinity and almost no impurity peak of other substances as can be seen from fig. 4 b. Fig. 5a shows that the waste graphite of the reassembled battery after lithium extraction has 338mA/g at the multiplying power of 0.1C, and fig. 5b shows that the reversible capacity of the waste graphite at the large multiplying power of 1C is close to 300mA/g, and the capacity is significantly higher than that of the conventional commercial graphite. Fig. 6 shows that the waste graphite subjected to steam heat treatment is used for the sodium ion half-cell after ball milling, and performance tests show that the first coulombic efficiency of the waste graphite is 80.1%, and the capacity of 203mAh/g can be obtained under the high multiplying power of 1000mA/g (fig. 6 shows that water is used for punching). The reversible capacity of the sample is higher than that of the original waste graphite directly ball-milled at a low multiplying power (no hole is formed in figure 6), which shows that more defects and functional groups can be introduced on the graphite surface through the steam heat treatment, so that more sodium ions can be stored. In fig. 7, the XRD spectrum shows that the lithium iron phosphate material prepared again has high crystallinity and few impurity peaks; after the lithium ion battery is assembled, the reversible capacity of about 150mA/g is possessed under the multiplying power of 0.1C (figure 8a), and meanwhile, the lithium ion battery has better multiplying power performance (figure 8 b).
Example 2
The preparation process of example 2 was substantially the same as that of example 1 except that the heating temperature in step (1) was changed to 400 ℃. The graphite residue of the lithium-rich graphite after the heat treatment in example 2 was 87.1%, the content of lithium element in the delithiated positive electrode obtained by the ICP test was 6.2%, and the extraction efficiency with deionized water was 98.4%.
Example 3
The preparation process of example 3 was substantially the same as that of example 1 except that the heating temperature in step (1) was changed to 900 ℃. Example 3 after the heat treatment in step (1), the graphite residue of the lithium-rich graphite after the heat treatment is only 5.1%, the graphite is completely burnt at the temperature, a small amount of white lithium-containing compound remains, lithium is selectively extracted based on the lithium intercalation graphite, the graphite recovery is considered, and the economic value of the high-temperature treatment at 900 ℃ is low.
Example 4
Example 4 is substantially the same as example 1 except that the time for ultrasonic lithium extraction in step (2) was changed to 40min, and the extraction efficiency with deionized water was 88.2%.
Example 5
Example 5 is substantially the same as example 1 except that the time for ultrasonic lithium extraction in step (2) was changed to 70min, and the extraction efficiency with deionized water was 99.9%.
Comparative example 1
Comparative example 1 was prepared substantially the same as example 1, except that no water vapor treatment was added to the lithium intercalated graphite in step (1). The graphite residual amount of the lithium-rich graphite after the heat treatment is 81.5%, the content of lithium element is 6.6% by ICP test, and the extraction efficiency by using deionized water reaches 99.3%.
Comparative example 2
The preparation method of comparative example 2 is substantially the same as that of example 1, except that the heating step in step (1) is not required after the negative electrode lithium intercalated graphite is obtained in step (1), and the negative electrode lithium intercalated graphite is directly used for lithium recovery in the subsequent step (2) and ball milling in step (3). The content of lithium element in lithium-rich graphite (recovered graphite) is 6.1% through ICP test, the extraction efficiency of deionized water reaches 98.4%, 80.1% of first coulombic efficiency of a sodium ion battery can be obtained by directly ball-milling initial graphite, the reversible capacity is 170mAh/g (recovered waste graphite in figure 6-without punching) under the high multiplying power of 1000mA/g, and the lower capacity is attributed to the fact that the surface defects and the content of functional groups of the ball-milled graphite are lower than those of the ball-milled graphite subjected to water vapor co-heat treatment.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that the waste battery is completely discharged and then disassembled in step (1). ICP tests show that the content of lithium in the initial discharge waste battery negative electrode graphite is 1.4%, the residual rate of the lithium-rich graphite after steam heat treatment is 80.6%, the content of the lithium in the graphite is 3.0% through the ICP tests, and the extraction efficiency of deionized water is 99.9%.
Comparative example 4
Comparative example 4 the manufacturing method of example 1 was substantially the same as that of example except that the waste battery was completely discharged in step (1) and the heating process was not carried out using a steam co-heating process. ICP test shows that the content of lithium element in the lithium-rich graphite after heat treatment is 1.6%, and the extraction efficiency of deionized water reaches 99.8%.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. A method for recycling and reusing anodes and cathodes of waste batteries is characterized by comprising the following steps:
(1) disassembling the waste battery to obtain a lithium-removed positive electrode and a lithium-intercalated graphite negative electrode, then placing the lithium-intercalated graphite negative electrode in a reaction container, and then introducing water vapor and protective gas for carrying out co-heat treatment to obtain heat-treated lithium-rich graphite;
(2) soaking the lithium-rich graphite subjected to heat treatment in the step (1) in water, performing ultrasonic treatment, filtering and separating filtrate and filter residue, concentrating the filtrate, and drying to obtain a lithium source, wherein the filter residue is graphite subjected to lithium extraction;
(3) uniformly mixing the lithium source obtained in the step (2), the lithium-removing anode obtained in the step (1) and a carbon source to obtain a mixture, and heating for calcination treatment to obtain a lithium iron phosphate anode;
(4) and (3) using the graphite subjected to lithium extraction in the step (2) to prepare a lithium ion battery or preparing a negative electrode material of a sodium ion battery after ball milling treatment.
2. The method for recycling and reusing the positive electrode and the negative electrode of the waste battery according to claim 1, wherein the waste battery in the step (1) is a lithium battery, the positive electrode material of the waste battery is lithium iron phosphate, and the negative electrode material of the waste battery is graphite; the lithium battery is one of a hard shell lithium battery, a soft package lithium battery and a box type lithium battery.
3. The method for recycling and reusing the positive and negative electrodes of waste batteries according to claim 1, wherein in the step (1), the relative humidity of air is less than 10% when the waste batteries are disassembled.
4. The method for recycling and reusing the positive and negative electrodes of waste batteries according to claim 1, wherein the protective gas in the step (1) is one of argon and nitrogen; the water vapor is generated by passing water through a peristaltic pump and then through a steam generator.
5. The method for recycling and reusing the positive and negative electrodes of waste batteries according to claim 4, wherein the water replenishing rate of the peristaltic pump is 0.02-0.5 mL/min.
6. The method for recycling and reusing the anode and cathode of the waste battery as claimed in claim 1, wherein the temperature of the co-heat treatment in the step (1) is 400-900 ℃, and the time of the co-heat treatment is 1-2.5 h.
7. The method for recycling and reusing the positive and negative electrodes of the waste batteries according to claim 1, wherein the mass-to-volume ratio of the lithium-rich graphite subjected to the heat treatment in the step (2) to water is 1:20-1:80 g/mL; the power of ultrasonic treatment is 80-120W, and the time of ultrasonic treatment is 40-70 min.
8. The method for recycling and reusing the positive and negative electrodes of the waste batteries according to claim 1, wherein the carbon source in the step (3) is one or more of glucose, sucrose and citric acid; the mass ratio of the lithium source to the lithium removal anode is 1:2-1: 4; the mass ratio of the delithiation anode to the carbon source is 1:1.8-1: 3.
9. The method for recycling and reusing the positive and negative electrodes of waste batteries according to claim 1, wherein the calcination treatment in step (3) comprises: pre-burning for 2.5-3.5h at the temperature of 280-320 ℃ and then calcining for 9-11h at the temperature of 700-800 ℃.
10. The method for recycling and reusing the anode and cathode of the waste battery as claimed in any one of claims 1 to 9, wherein the rotation speed of the ball milling treatment in the step (4) is 300-500rpm, the time of the ball milling treatment is 12-72 hours, and the ball-to-material ratio of the ball milling treatment is 80:1-120: 1.
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