CN111883772A - Regenerated graphite electrode material and preparation method and application thereof - Google Patents

Regenerated graphite electrode material and preparation method and application thereof Download PDF

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CN111883772A
CN111883772A CN202010561954.5A CN202010561954A CN111883772A CN 111883772 A CN111883772 A CN 111883772A CN 202010561954 A CN202010561954 A CN 202010561954A CN 111883772 A CN111883772 A CN 111883772A
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graphite
electrode material
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waste
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黄云辉
伽龙
杨丹
马明远
杨莹
杜浩然
陈筱
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Tongji University
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C01B32/215—Purification; Recovery or purification of graphite formed in iron making, e.g. kish graphite
    • 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
    • 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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    • 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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Abstract

The invention relates to a preparation method of a regenerated graphite electrode material, the regenerated graphite electrode material obtained by the preparation method and application, wherein the preparation method specifically comprises the following steps: (a) placing the waste battery in a salt solution for discharging, and sequentially performing primary drying, disassembly and stripping after discharging to obtain waste graphite; (b) mixing the waste graphite obtained in the step (a) with a reaction solvent, and reacting to obtain a reaction solution; (c) and (c) carrying out suction filtration on the reaction liquid obtained in the step (b) to obtain a crude graphite product, and carrying out secondary drying on the crude graphite product to obtain the regenerated graphite electrode material. Compared with the prior art, the regenerated graphite electrode material prepared by the invention recovers a good layered structure, is beneficial to the insertion and the separation of lithium ions in the charging and discharging processes of a battery, simultaneously removes impurities among graphite layers, dredges a transmission channel of the lithium ions, increases the structural stability and ensures the cycle performance of the battery.

Description

Regenerated graphite electrode material and preparation method and application thereof
Technical Field
The invention relates to the field of resource regeneration, in particular to a regenerated graphite electrode material and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high energy density, high output voltage, good cycle performance and the like, and is widely applied to various fields of electric vehicles, portable electronic products, large power supplies and the like. With the rapid development of electric vehicles, China faces large-scale decommissioning of batteries, and if waste batteries are not properly recycled, great resource waste and environmental pollution are caused.
The lithium ion battery mainly comprises a positive electrode material, a diaphragm, an electrolyte, a negative electrode material and the like, wherein graphite is very suitable for the insertion and the separation of lithium ions in the charging and discharging processes due to the characteristics of good conductivity, high degree of crystallization, good layered structure and the like, so that the graphite becomes the most widely applied negative electrode material at present. In order to recover the graphite cathode, researchers provide recovery technologies such as high-temperature metallurgy and wet metallurgy, but the recovery technologies have the problems of complex process, use of harmful chemical substances or need of high temperature and the like, so that more serious environmental pollution is easily caused, and the economic value of the regenerated graphite is reduced.
At present, graphite recovered from waste batteries is widely applied to various fields, such as preparation of high-performance graphene or application of the high-performance graphene as a catalyst, a wastewater adsorbent and the like, and the recovered and regenerated graphite is reused as a negative electrode material of a lithium ion battery in the invention to show good electrochemical performance. Therefore, it is necessary to develop a more green and efficient graphite recycling technology for the sustainable development strategy of our country.
Disclosure of Invention
The invention aims to solve the problems and provide a preparation method of a regenerated graphite electrode material, the regenerated graphite electrode material obtained by the preparation method and application thereof.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a regenerated graphite electrode material specifically comprises the following steps:
(a) placing the waste battery in a salt solution for discharging, and sequentially performing primary drying, disassembling and stripping after discharging to obtain waste graphite, wherein the disassembling can be performed by adopting ceramic scissors, and the stripping refers to stripping a graphite cathode from a current collector such as a copper foil;
(b) mixing the waste graphite obtained in the step (a) with a reaction solvent, and reacting to obtain a reaction solution, wherein the reaction solution is a suspension, and the reaction solvent and substances such as residual lithium, soluble lithium salt and the like in the waste graphite undergo a redox reaction and have a function of dissolving lithium salt;
(c) and (c) carrying out suction filtration on the reaction liquid obtained in the step (b) to obtain a crude graphite product, and carrying out secondary drying on the crude graphite product to obtain the regenerated graphite electrode material.
Preferably, in the step (a), the salt solution is a sodium chloride solution, and the mass concentration of the sodium chloride solution is 5-26.5%.
Preferably, in the step (a), the discharging time is 8-12h, the temperature of the first drying is 50-70 ℃, and the time of the first drying is 8-12 h. Further preferably, in the step (a), the discharge time is 10h, the temperature of the first drying is 60 ℃, and the time of the first drying is 10 h.
Preferably, in the step (a), the stripping is selected from manual stripping or sintering stripping, the temperature of the sintering stripping is 400-600 ℃, preferably 400 ℃, the time of the sintering stripping is 2-4h, and the temperature rise rate is 1-10 ℃/min. The manual stripping is to strip graphite from the current collector by using a tool such as a blade, and the atmosphere for sintering stripping is selected from air, nitrogen or 5% H2One or more of the mixed gas of/Ar.
Preferably, in step (b), the reaction solvent is selected from one or more of water, ethanol, N-dimethylformamide, sulfuric acid, hydrochloric acid or nitric acid. Further preferably, the reaction solvent is deionized water. Wherein, except deionized water, the molar concentration of other reaction solvents is 0.5-4 mol/L.
Preferably, in the step (c), when the reaction solvent is an acidic substance, the pH value of the reaction solution is adjusted to be neutral during the suction filtration. The pH value adjustment refers to that the acidic reaction solution is diluted to be neutral by increasing the times of water washing and suction filtration.
Preferably, in the step (b), the solid-to-liquid ratio of the waste graphite to the reaction solvent is 1-100 g/L.
Preferably, in the step (b), ultrasonic dispersion or stirring dispersion is carried out during the reaction process, the power of ultrasonic is 50-150W, the rotating speed of stirring is 350-450rpm, and the reaction time is 0.5-2 h. Further preferably, the power of the ultrasound is 100W, the rotation speed of the stirring is 400rpm, and the reaction time is 0.5 h. The ultrasound was performed in an ultrasound instrument, and the stirring was performed using a magnetic stirrer.
Preferably, in step (c), the suction filtration is carried out under vacuum for 0.5-1 h. During suction filtration, medium-speed filter paper with the diameter of 80mm is paved on a Buchner funnel, a filter liquor bottle is connected below the funnel, the Buchner funnel is connected with a vacuum circulating water pump through a rubber tube for suction filtration, and a reaction solvent and graphite are separated.
Preferably, in step (c), the second drying is performed under vacuum at 60-100 deg.C for 6-10 h.
The regenerated graphite electrode material prepared by the preparation method is adopted.
The regenerated graphite electrode material is applied to a battery. The regenerated graphite electrode material prepared by the method, the super conductive carbon black and the LA133 adhesive are ground and uniformly mixed according to the mass ratio of 8:1:1, deionized water is added to prepare uniform slurry, the uniform slurry is coated on an aluminum foil, the aluminum foil is dried in an oven at 80 ℃ for 10 hours, and then a pole piece with the diameter of 8mm is pressed. A 2025 button cell is assembled in a glove box in high-purity argon atmosphere by using a metal lithium sheet as a cathode (the purity of argon is more than 99.99 percent, H)2O content less than 1ppm, O2The content is less than 3 ppm).
Compared with the recycled untreated graphite, the regenerated graphite electrode material prepared by the invention recovers the good layered structure, is beneficial to the insertion and separation of lithium ions in the charging and discharging processes of the battery, removes impurities among graphite layers, dredges the transmission channel of the lithium ions, increases the structural stability, ensures the cycle performance of the battery, and has high specific capacity and charging and discharging efficiency when being used as a negative electrode material of the lithium ion battery. Under the current density of 0.1C, the specific capacity of the recycled untreated graphite is 95.4mAh/g, and the specific capacity of the regenerated graphite electrode material reaches 312 mAh/g. The preparation method provided by the invention has the advantages of low price of the used solvent, rich sources, simple pretreatment, no toxicity, greenness, environmental protection and good performance, and the product can be directly applied to the lithium ion battery.
Drawings
FIG. 1 is a graph comparing the X-ray powder diffraction (XRD) of the recycled, untreated graphite scrap material from example 1 and comparative example 1;
fig. 2 is a comparison graph of the first-turn charge-discharge curves (0.1C magnification) of the 2025-type button cell prepared in example 1 and the 2025-type button cell prepared in comparative example 1;
fig. 3 is a graph comparing the specific discharge capacity versus cycle number curves (0.1C rate) for the 2025 type button cell made in example 1 and the 2025 type button cell made in comparative example 1;
fig. 4 is a graph comparing the specific charge capacity versus cycle number curves (0.1C rate) for the 2025-type button cell made in example 1 and the 2025-type button cell made in comparative example 1;
fig. 5 is a graph comparing the charge and discharge efficiency curves (0.1C rate) for the 2025 type button cell made in example 1 and the 2025 type button cell made in comparative example 1;
fig. 6 is a graph comparing the rate discharge curves of the 2025-type button cell made in example 1 and the 2025-type button cell made in comparative example 1.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
A regenerated graphite electrode material is prepared by a preparation method comprising the following steps:
(1) placing the waste batteries in a sodium chloride solution with the mass fraction of 5% for discharging for 10h, then drying the waste batteries for the first time, placing the batteries in a drying oven at 60 ℃ for drying for 10h, and then disassembling the batteries by using ceramic scissors;
(2) the graphite negative electrode is processed by a manual stripping method: scraping graphite off a current collector by using a blade to obtain waste graphite which is powdery;
(3) mixing deionized water with the waste graphite obtained in the step (2) according to a solid-to-liquid ratio of 10g/L, stirring for 0.5h on a magneton stirrer at a rotating speed of 400rpm, and reacting to obtain a reaction liquid which is a suspension;
(4) after the reaction is finished, paving medium-speed filter paper with the diameter of 80mm on a Buchner funnel, carrying out vacuum filtration on the suspension obtained in the step (3), repeating the step (3) on the obtained filter residue for three times, and carrying out vacuum filtration for 30min each time to obtain a treated crude graphite product;
(5) and (4) carrying out secondary drying on the crude graphite product obtained in the step (4) by using a vacuum drying oven, and drying at the temperature of 80 ℃ for 8h to obtain the regenerated graphite electrode material. An X-ray powder diffraction (XRD) pattern of the regenerated Graphite electrode material is shown in figure 1, and the regenerated Graphite electrode material corresponds to a PDF #41-1487Graphite-2H crystal phase in a PDF card, shows diffraction peaks on crystal planes (002), (101) and (004), wherein the diffraction peak corresponding to the crystal plane (002) is strong and sharp in peak shape, so that the material has good crystallinity, shows a regular layered structure, has no redundant impurity peak, and shows that the material has high chemical component purity and no impurity.
The regenerated graphite electrode material prepared by the method, the super conductive carbon black and the LA133 adhesive are ground and uniformly mixed according to the mass ratio of 8:1:1, deionized water is added to prepare uniform slurry, the uniform slurry is coated on an aluminum foil, the aluminum foil is dried in an oven at 80 ℃ for 10 hours, and then a pole piece with the diameter of 8mm is pressed. A 2025 button cell is assembled in a glove box in high-purity argon atmosphere by using a metal lithium sheet as a cathode (the purity of argon is more than 99.99 percent, H)2O content less than 1ppm, O2Content less than 3ppm), a first-turn charge-discharge curve chart of the 2025 type button cell under 0.1C multiplying power is shown in fig. 2, a discharge specific capacity and cycle frequency curve chart under 0.1C multiplying power is shown in fig. 3, a charge specific capacity and cycle frequency curve chart under 0.1C multiplying power is shown in fig. 4, a charge-discharge efficiency curve chart under 0.1C multiplying power is shown in fig. 5, and a multiplying power discharge curve chart is shown in fig. 6. As can be seen from fig. 2, the battery of example 1 can rapidly discharge at a low voltage, and the specific discharge capacity can reach 300mAh/g or more, whereas the battery of comparative example 1 can start to discharge at a voltage of 0.25V, and the specific discharge capacity is less than 100 mAh/g; as can be seen from fig. 3 and 4, the graphite electrode obtained in example 1 shows a relatively smooth charge-discharge cycle after being cycled 45 times at a current density of 0.1C, and the discharge capacity reaches above 290mAh/g, indicating that the electrode has stable electrochemical performance along with the progress of battery charge-discharge, while the graphite electrode in comparative example 1 has a discharge curve and a charge curve that are not smooth and the discharge capacity is only about 100mAh/g, indicating that the electrode cannot perform stable charge-discharge cycle; in addition, as can be seen from fig. 5 and 6, although the charge and discharge efficiency graphs of the materials obtained in example 1 and comparative example 1 are all maintained at 90% or more, it is obvious from fig. 6 that the graphite electrode after water washing of example 1 has more stable rate capability under different current densities of 0.05C, 0.1C, 0.2C, 0.5C, 1C and 2C, and when the current density is reduced to an initial value of 0.05C, the discharge capacity of the water-washed graphite electrode can still reach 330mAh/g, and the discharge capacity of the water-washed graphite electrode can still reach 330mAh/gThe cycle was maintained for a long time, whereas the graphite electrode of comparative example 1 had a lower discharge capacity and could not be maintained for a long time. Therefore, compared with the graphite which is not treated after circulation, the regenerated graphite after water washing has larger charging and discharging capacity and more stable working performance.
Example 2
A regenerated graphite electrode material is prepared by a preparation method comprising the following steps:
(1) placing the waste batteries in a saturated sodium chloride solution for discharging for 10h, then drying the waste batteries for the first time, placing the dried batteries in a drying oven at 60 ℃ for drying for 10h, and then disassembling the batteries by using ceramic scissors;
(2) the graphite negative electrode is processed by a manual stripping method: scraping graphite off a current collector by using a blade to obtain waste graphite which is powdery;
(3) mixing deionized water with the waste graphite obtained in the step (2) according to a solid-to-liquid ratio of 10g/L, stirring for 0.5h on a magneton stirrer at a rotating speed of 400rpm, and reacting to obtain a reaction liquid which is a suspension;
(4) after the reaction is finished, paving medium-speed filter paper with the diameter of 80mm on a Buchner funnel, carrying out vacuum filtration on the suspension obtained in the step (3), repeating the step (3) on the obtained filter residue for three times, and carrying out vacuum filtration for 30min each time to obtain a treated crude graphite product;
(5) and (4) carrying out secondary drying on the crude graphite product obtained in the step (4) by using a vacuum drying oven, and drying at the temperature of 80 ℃ for 8h to obtain the regenerated graphite electrode material.
The graphite electrode material prepared by the method, the super conductive carbon black and the LA133 adhesive are ground and uniformly mixed according to the mass ratio of 8:1:1, deionized water is added to prepare uniform slurry, the uniform slurry is coated on an aluminum foil, the aluminum foil is dried in an oven at 80 ℃ for 10 hours, and then a pole piece with the diameter of 8mm is pressed. A 2025 button cell is assembled in a glove box in high-purity argon atmosphere by using a metal lithium sheet as a cathode (the purity of argon is more than 99.99 percent, H)2O content less than 1ppm, O2The content is less than 3 ppm). At the current density of 0.1C, the specific capacity of the battery is 310mAh/g, and the specific capacity does not obviously decrease after 100 times of circulation.
Example 3
A regenerated graphite electrode material is prepared by a preparation method comprising the following steps:
(1) placing the waste batteries in a sodium chloride solution with the mass fraction of 5% for discharging for 10h, then drying the waste batteries for the first time, placing the batteries in a drying oven at 60 ℃ for drying for 10h, and then disassembling the batteries by using ceramic scissors;
(2) heating the graphite cathode to 400 ℃ at the heating rate of 5 ℃/min in the air atmosphere, keeping the temperature for 2 hours, and then stripping graphite from a current collector to obtain waste graphite in powder form;
(3) mixing deionized water with the waste graphite obtained in the step (2) according to a solid-to-liquid ratio of 10g/L, stirring for 0.5h on a magneton stirrer at a rotating speed of 400rpm, and reacting to obtain a reaction liquid which is a suspension;
(4) after the reaction is finished, paving medium-speed filter paper with the diameter of 80mm on a Buchner funnel, carrying out vacuum filtration on the suspension obtained in the step (3), repeating the step (3) on the obtained filter residue for three times, and carrying out suction filtration for 60min each time to obtain a treated crude graphite product;
(5) and (4) carrying out secondary drying on the crude graphite product obtained in the step (4) by using a vacuum drying oven, and drying at the temperature of 80 ℃ for 8h to obtain the regenerated graphite electrode material.
The graphite electrode material prepared by the method, the super conductive carbon black and the LA133 adhesive are ground and uniformly mixed according to the mass ratio of 8:1:1, deionized water is added to prepare uniform slurry, the uniform slurry is coated on an aluminum foil, the aluminum foil is dried in an oven at 80 ℃ for 10 hours, and then a pole piece with the diameter of 8mm is pressed. A 2025 button cell is assembled in a glove box in high-purity argon atmosphere by using a metal lithium sheet as a cathode (the purity of argon is more than 99.99 percent, H)2O content less than 1ppm, O2The content is less than 3 ppm). At the current density of 0.1C, the specific capacity of the battery is 315mAh/g, and the specific capacity does not obviously decrease after 100 times of circulation.
Example 4
A regenerated graphite electrode material is prepared by a preparation method comprising the following steps:
(1) placing the waste batteries in a sodium chloride solution with the mass fraction of 5% for discharging for 10h, then drying the waste batteries for the first time, placing the batteries in a drying oven at 60 ℃ for drying for 10h, and then disassembling the batteries by using ceramic scissors;
(2) heating the graphite cathode to 400 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, keeping the temperature for 2 hours, and then stripping graphite from a current collector to obtain waste graphite in powder form;
(3) mixing deionized water with the waste graphite obtained in the step (2) according to a solid-to-liquid ratio of 10g/L, stirring for 0.5h on a magneton stirrer at a rotating speed of 400rpm, and reacting to obtain a reaction liquid which is a suspension;
(4) after the reaction is finished, paving medium-speed filter paper with the diameter of 80mm on a Buchner funnel, carrying out vacuum filtration on the suspension obtained in the step (3), repeating the step (3) on the obtained filter residue for three times, and carrying out vacuum filtration for 30min each time to obtain a treated crude graphite product;
(5) and (4) carrying out secondary drying on the crude graphite product obtained in the step (4) by using a vacuum drying oven, and drying at the temperature of 80 ℃ for 8h to obtain the regenerated graphite electrode material.
The graphite electrode material prepared by the method, the super conductive carbon black and the LA133 adhesive are ground and uniformly mixed according to the mass ratio of 8:1:1, deionized water is added to prepare uniform slurry, the uniform slurry is coated on an aluminum foil, the aluminum foil is dried in an oven at 80 ℃ for 10 hours, and then a pole piece with the diameter of 8mm is pressed. A 2025 button cell is assembled in a glove box in high-purity argon atmosphere by using a metal lithium sheet as a cathode (the purity of argon is more than 99.99 percent, H)2O content less than 1ppm, O2The content is less than 3 ppm). At the current density of 0.1C, the specific capacity of the battery is 309mAh/g, and the specific capacity does not obviously decrease after 100 times of circulation.
Example 5
A regenerated graphite electrode material is prepared by a preparation method comprising the following steps:
(1) placing the waste batteries in a sodium chloride solution with the mass fraction of 5% for discharging for 10h, then drying the waste batteries for the first time, placing the batteries in a drying oven at 60 ℃ for drying for 10h, and then disassembling the batteries by using ceramic scissors;
(2) heating the graphite cathode to 500 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, keeping the temperature for 2 hours, and then stripping graphite from a current collector to obtain waste graphite in powder form;
(3) mixing deionized water with the waste graphite obtained in the step (2) according to a solid-to-liquid ratio of 10g/L, stirring for 0.5h on a magneton stirrer at a rotating speed of 400rpm, and reacting to obtain a reaction liquid which is a suspension;
(4) after the reaction is finished, paving medium-speed filter paper with the diameter of 80mm on a Buchner funnel, carrying out vacuum filtration on the suspension obtained in the step (3), repeating the step (3) on the obtained filter residue for three times, and carrying out vacuum filtration for 30min each time to obtain a treated crude graphite product;
(5) and (5) drying the crude graphite product obtained in the step (4) for 8 hours at the temperature of 80 ℃ by using a vacuum drying oven to obtain the regenerated graphite electrode material.
The graphite electrode material prepared by the method, the super conductive carbon black and the LA133 adhesive are ground and uniformly mixed according to the mass ratio of 8:1:1, deionized water is added to prepare uniform slurry, the uniform slurry is coated on an aluminum foil, the aluminum foil is dried in an oven at 80 ℃ for 10 hours, and then a pole piece with the diameter of 8mm is pressed. A 2025 button cell is assembled in a glove box in high-purity argon atmosphere by using a metal lithium sheet as a cathode (the purity of argon is more than 99.99 percent, H)2O content less than 1ppm, O2The content is less than 3 ppm). At the current density of 0.1C, the specific capacity of the battery is 310mAh/g, and the specific capacity does not obviously decrease after 100 times of circulation.
Example 6
A regenerated graphite electrode material is prepared by a preparation method comprising the following steps:
(1) placing the waste batteries in a sodium chloride solution with the mass fraction of 5% for discharging for 10h, then drying the waste batteries for the first time, placing the batteries in a drying oven at 60 ℃ for drying for 10h, and then disassembling the batteries by using ceramic scissors;
(2) heating the graphite cathode to 600 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, keeping the temperature for 2 hours, and then stripping graphite from a current collector to obtain waste graphite in powder form;
(3) mixing deionized water with the waste graphite obtained in the step (2) according to a solid-to-liquid ratio of 10g/L, stirring for 0.5h on a magneton stirrer at a rotating speed of 400rpm, and reacting to obtain a reaction liquid which is a suspension;
(4) after the reaction is finished, paving medium-speed filter paper with the diameter of 80mm on a Buchner funnel, carrying out vacuum filtration on the suspension obtained in the step (3), repeating the step (3) on the obtained filter residue for three times, and carrying out vacuum filtration for 30min each time to obtain a treated crude graphite product;
(5) and (4) carrying out secondary drying on the crude graphite product obtained in the step (4) by using a vacuum drying oven, and drying at the temperature of 80 ℃ for 8h to obtain the regenerated graphite electrode material.
The graphite electrode material prepared by the method, the super conductive carbon black and the LA133 adhesive are ground and uniformly mixed according to the mass ratio of 8:1:1, deionized water is added to prepare uniform slurry, the uniform slurry is coated on an aluminum foil, the aluminum foil is dried in an oven at 80 ℃ for 10 hours, and then a pole piece with the diameter of 8mm is pressed. A 2025 button cell is assembled in a glove box in high-purity argon atmosphere by using a metal lithium sheet as a cathode (the purity of argon is more than 99.99 percent, H)2O content less than 1ppm, O2The content is less than 3 ppm). At the current density of 0.1C, the specific capacity of the battery is 308mAh/g, and the specific capacity does not obviously decrease after 100 times of circulation.
Example 7
A regenerated graphite electrode material is prepared by a preparation method comprising the following steps:
(1) placing the waste batteries in a sodium chloride solution with the mass fraction of 5% for discharging for 10h, then drying the waste batteries for the first time, placing the batteries in a drying oven at 60 ℃ for drying for 10h, and then disassembling the batteries by using ceramic scissors;
(2) the graphite negative electrode is processed by a manual stripping method: scraping graphite off a current collector by using a blade to obtain waste graphite which is powdery;
(3) mixing ethanol and the waste graphite obtained in the step (2) according to a solid-to-liquid ratio of 10g/L, stirring for 0.5h on a magneton stirrer at a rotating speed of 400rpm, and reacting to obtain a reaction liquid which is a suspension;
(4) after the reaction is finished, paving medium-speed filter paper with the diameter of 80mm on a Buchner funnel, carrying out vacuum filtration on the suspension obtained in the step (3), repeating the step (3) on the obtained filter residue for three times, and carrying out vacuum filtration for 30min each time to obtain a treated crude graphite product;
(5) and (4) carrying out secondary drying on the crude graphite product obtained in the step (4) by using a vacuum drying oven, and drying at the temperature of 80 ℃ for 8h to obtain the regenerated graphite electrode material.
The graphite electrode material prepared by the method, the super conductive carbon black and the LA133 adhesive are ground and uniformly mixed according to the mass ratio of 8:1:1, deionized water is added to prepare uniform slurry, the uniform slurry is coated on an aluminum foil, the aluminum foil is dried in an oven at 80 ℃ for 10 hours, and then a pole piece with the diameter of 8mm is pressed. A 2025 button cell is assembled in a glove box in high-purity argon atmosphere by using a metal lithium sheet as a cathode (the purity of argon is more than 99.99 percent, H)2O content less than 1ppm, O2The content is less than 3 ppm). At the current density of 0.1C, the specific capacity of the battery is 308mAh/g, and the specific capacity does not obviously decrease after 100 times of circulation.
Example 8
A regenerated graphite electrode material is prepared by a preparation method comprising the following steps:
(1) placing the waste batteries in a sodium chloride solution with the mass fraction of 5% for discharging for 10h, then drying the waste batteries for the first time, placing the batteries in a drying oven at 60 ℃ for drying for 10h, and then disassembling the batteries by using ceramic scissors;
(2) the graphite negative electrode is processed by a manual stripping method: scraping graphite off a current collector by using a blade to obtain waste graphite which is powdery;
(3) mixing 1mol/L hydrochloric acid with the waste graphite obtained in the step (2) according to a solid-to-liquid ratio of 10g/L, stirring for 0.5h on a magneton stirrer at a rotating speed of 400rpm, and reacting to obtain a reaction liquid which is a suspension;
(4) after the reaction is finished, paving medium-speed filter paper with the diameter of 80mm on a Buchner funnel, performing vacuum filtration on the suspension obtained in the step (3), and washing the obtained filter residue with deionized water until the pH value of the filtrate is 7 to obtain a treated crude graphite product;
(5) and (4) carrying out secondary drying on the crude graphite product obtained in the step (4) by using a vacuum drying oven, and drying at the temperature of 80 ℃ for 8h to obtain the regenerated graphite electrode material.
The graphite electrode material prepared by the method, the super conductive carbon black and the LA133 adhesive are ground and uniformly mixed according to the mass ratio of 8:1:1, deionized water is added to prepare uniform slurry, the uniform slurry is coated on an aluminum foil, the aluminum foil is dried in an oven at 80 ℃ for 10 hours, and then a pole piece with the diameter of 8mm is pressed. A 2025 button cell is assembled in a glove box in high-purity argon atmosphere by using a metal lithium sheet as a cathode (the purity of argon is more than 99.99 percent, H)2O content less than 1ppm, O2The content is less than 3 ppm). At the current density of 0.1C, the specific capacity of the battery is 320mAh/g, and the specific capacity does not obviously decrease after 100 times of circulation.
Example 9
A regenerated graphite electrode material is prepared by a preparation method comprising the following steps:
(1) placing the waste batteries in a sodium chloride solution with the mass fraction of 5% for discharging for 10h, then drying the waste batteries for the first time, placing the batteries in a drying oven at 60 ℃ for drying for 10h, and then disassembling the batteries by using ceramic scissors;
(2) the graphite negative electrode is processed by a manual stripping method: scraping graphite off a current collector by using a blade to obtain waste graphite which is powdery;
(3) mixing 2mol/L hydrochloric acid with the waste graphite obtained in the step (2) according to a solid-to-liquid ratio of 10g/L, stirring for 0.5h on a magneton stirrer at a rotating speed of 400rpm, and reacting to obtain a reaction liquid which is a suspension;
(4) after the reaction is finished, paving medium-speed filter paper with the diameter of 80mm on a Buchner funnel, performing suction filtration on the suspension obtained in the step (3), and washing the obtained filter residue with deionized water until the pH value of the filtrate is 7 to obtain a treated crude graphite product;
(5) and (4) carrying out secondary drying on the crude graphite product obtained in the step (4) by using a vacuum drying oven, and drying at the temperature of 80 ℃ for 8h to obtain the regenerated graphite electrode material.
The graphite electrode material prepared by the invention and the super conductive carbonGrinding and uniformly mixing the black and LA133 adhesives according to the mass ratio of 8:1:1, adding deionized water to prepare uniform slurry, coating the uniform slurry on an aluminum foil, drying the aluminum foil in an oven at 80 ℃ for 10 hours, and pressing the aluminum foil and the LA133 adhesives into a pole piece with the diameter of 8 mm. A 2025 button cell is assembled in a glove box in high-purity argon atmosphere by using a metal lithium sheet as a cathode (the purity of argon is more than 99.99 percent, H)2O content less than 1ppm, O2The content is less than 3 ppm). At the current density of 0.1C, the specific capacity of the battery is 316mAh/g, and the specific capacity does not obviously decrease after 100 times of circulation.
Example 10
A regenerated graphite electrode material is prepared by a preparation method comprising the following steps:
(1) placing the waste batteries in a sodium chloride solution with the mass fraction of 5% for discharging for 10h, then drying the waste batteries for the first time, placing the batteries in a drying oven at 60 ℃ for drying for 10h, and then disassembling the batteries by using ceramic scissors;
(2) the graphite negative electrode is processed by a manual stripping method: scraping graphite off a current collector by using a blade to obtain waste graphite which is powdery;
(3) mixing 1mol/L sulfuric acid with the waste graphite obtained in the step (2) according to a solid-to-liquid ratio of 10g/L, stirring for 0.5h on a magneton stirrer at a rotating speed of 400rpm, and reacting to obtain a reaction liquid which is a suspension;
(4) after the reaction is finished, paving medium-speed filter paper with the diameter of 80mm on a Buchner funnel, performing vacuum filtration on the suspension obtained in the step (3), and washing the obtained filter residue with deionized water until the pH value of the filtrate is 7 to obtain a treated crude graphite product;
(5) and (4) carrying out secondary drying on the crude graphite product obtained in the step (4) by using a vacuum drying oven, and drying at the temperature of 80 ℃ for 8h to obtain the regenerated graphite electrode material.
The graphite electrode material prepared by the method, the super conductive carbon black and the LA133 adhesive are ground and uniformly mixed according to the mass ratio of 8:1:1, deionized water is added to prepare uniform slurry, the uniform slurry is coated on an aluminum foil, the aluminum foil is dried in an oven at 80 ℃ for 10 hours, and then a pole piece with the diameter of 8mm is pressed. A metal lithium sheet is used as a negative electrode,assembling 2025 button cell in a glove box with high purity argon atmosphere (argon purity is more than 99.99%, H)2O content less than 1ppm, O2The content is less than 3 ppm). At the current density of 0.1C, the specific capacity of the battery is 307mAh/g, and the specific capacity does not obviously decrease after 100 times of circulation.
Example 11
A regenerated graphite electrode material is prepared by a preparation method comprising the following steps:
(1) placing the waste batteries in a sodium chloride solution with the mass fraction of 5% for discharging for 10h, then drying the waste batteries for the first time, placing the batteries in a drying oven at 60 ℃ for drying for 10h, and then disassembling the batteries by using ceramic scissors;
(2) the graphite negative electrode is processed by a manual stripping method: scraping graphite off a current collector by using a blade to obtain waste graphite which is powdery;
(3) mixing 2mol/L sulfuric acid with the waste graphite obtained in the step (2) according to a solid-to-liquid ratio of 10g/L, stirring for 0.5h on a magneton stirrer at a rotating speed of 400rpm, and reacting to obtain a reaction liquid which is a suspension;
(4) after the reaction is finished, paving medium-speed filter paper with the diameter of 80mm on a Buchner funnel, performing vacuum filtration on the suspension obtained in the step (3), and washing the obtained filter residue with deionized water until the pH value of the filtrate is 7 to obtain a treated crude graphite product;
(5) and (4) carrying out secondary drying on the crude graphite product obtained in the step (4) by using a vacuum drying oven, and drying at the temperature of 80 ℃ for 8h to obtain the regenerated graphite electrode material.
The graphite electrode material prepared by the method, the super conductive carbon black and the LA133 adhesive are ground and uniformly mixed according to the mass ratio of 8:1:1, deionized water is added to prepare uniform slurry, the uniform slurry is coated on an aluminum foil, the aluminum foil is dried in an oven at 80 ℃ for 10 hours, and then a pole piece with the diameter of 8mm is pressed. A 2025 button cell is assembled in a glove box in high-purity argon atmosphere by using a metal lithium sheet as a cathode (the purity of argon is more than 99.99 percent, H)2O content less than 1ppm, O2The content is less than 3 ppm). Under the current density of 0.1C, the specific capacity of the battery is 320mAh/g, and the battery is cycled for 100 timesThe amount does not decrease significantly.
Example 12
A regenerated graphite electrode material is prepared by a preparation method comprising the following steps:
(1) placing the waste batteries in a sodium chloride solution with the mass fraction of 5% for discharging for 10h, then drying the waste batteries for the first time, placing the batteries in a drying oven at 60 ℃ for drying for 10h, and then disassembling the batteries by using ceramic scissors;
(2) the graphite negative electrode is processed by a manual stripping method: scraping graphite off a current collector by using a blade to obtain waste graphite which is powdery;
(3) mixing deionized water with the waste graphite obtained in the step (2) according to a solid-to-liquid ratio of 20g/L, stirring for 0.5h on a magneton stirrer at a rotating speed of 400rpm, and reacting to obtain a reaction liquid which is a suspension;
(4) after the reaction is finished, paving medium-speed filter paper with the diameter of 80mm on a Buchner funnel, carrying out vacuum filtration on the suspension obtained in the step (3), repeating the step (3) on the obtained filter residue for three times, and carrying out vacuum filtration for 30mins each time to obtain a treated crude graphite product;
(5) and (4) carrying out secondary drying on the crude graphite product obtained in the step (4) by using a vacuum drying oven, and drying at the temperature of 80 ℃ for 8h to obtain the regenerated graphite electrode material.
The graphite electrode material prepared by the method, the super conductive carbon black and the LA133 adhesive are ground and uniformly mixed according to the mass ratio of 8:1:1, deionized water is added to prepare uniform slurry, the uniform slurry is coated on an aluminum foil, the aluminum foil is dried in an oven at 80 ℃ for 10 hours, and then a pole piece with the diameter of 8mm is pressed. A 2025 button cell is assembled in a glove box in high-purity argon atmosphere by using a metal lithium sheet as a cathode (the purity of argon is more than 99.99 percent, H)2O content less than 1ppm, O2The content is less than 3 ppm). At the current density of 0.1C, the specific capacity of the battery is 320mAh/g, and the specific capacity does not obviously decrease after 100 times of circulation.
Example 13
A regenerated graphite electrode material is prepared by a preparation method comprising the following steps:
(1) placing the waste batteries in a sodium chloride solution with the mass fraction of 5% for discharging for 10h, then drying the waste batteries for the first time, placing the batteries in a drying oven at 60 ℃ for drying for 10h, and then disassembling the batteries by using ceramic scissors;
(2) the graphite negative electrode is processed by a manual stripping method: scraping graphite off a current collector by using a blade to obtain waste graphite which is powdery;
(3) mixing deionized water with the waste graphite obtained in the step (2) according to a solid-liquid ratio of 10g/L, and carrying out ultrasonic treatment in an ultrasonic instrument with the power of 100W for 0.5h to obtain a reaction liquid, namely a suspension;
(4) after the reaction is finished, paving medium-speed filter paper with the diameter of 80mm on a Buchner funnel, carrying out vacuum filtration on the suspension obtained in the step (3), repeating the step (3) on the obtained filter residue for three times, and carrying out vacuum filtration for 30mins each time to obtain a treated crude graphite product;
(5) and (4) carrying out secondary drying on the crude graphite product obtained in the step (4) by using a vacuum drying oven, and drying at the temperature of 80 ℃ for 8h to obtain the regenerated graphite electrode material.
The graphite electrode material prepared by the method, the super conductive carbon black and the LA133 adhesive are ground and uniformly mixed according to the mass ratio of 8:1:1, deionized water is added to prepare uniform slurry, the uniform slurry is coated on an aluminum foil, the aluminum foil is dried in an oven at 80 ℃ for 10 hours, and then a pole piece with the diameter of 8mm is pressed. A 2025 button cell is assembled in a glove box in high-purity argon atmosphere by using a metal lithium sheet as a cathode (the purity of argon is more than 99.99 percent, H)2O content less than 1ppm, O2The content is less than 3 ppm). At the current density of 0.1C, the specific capacity of the battery is 312mAh/g, and the specific capacity does not obviously decrease after 100 times of circulation.
Example 14
A regenerated graphite electrode material is prepared by a preparation method comprising the following steps:
(1) placing the waste batteries in a sodium chloride solution with the mass fraction of 15% for discharging for 8h, then drying the waste batteries for the first time, placing the batteries in a 50 ℃ drying oven for drying for 12h, and then disassembling the batteries by using ceramic scissors;
(2) at 5% H2Mixed gas atmosphere of/ArHeating the graphite cathode to 600 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 2 hours, and then stripping graphite from a current collector to obtain waste graphite in powder form;
(3) mixing 2mol/L nitric acid and the waste graphite obtained in the step (2) according to a solid-to-liquid ratio of 1g/L, stirring for 2 hours on a magneton stirrer at a rotating speed of 350rpm, and reacting to obtain a reaction liquid which is a suspension;
(4) after the reaction is finished, paving medium-speed filter paper with the diameter of 80mm on a Buchner funnel, performing vacuum filtration on the suspension obtained in the step (3), and washing the obtained filter residue with deionized water until the pH value of the filtrate is 7 to obtain a treated crude graphite product;
(5) and (4) carrying out secondary drying on the crude graphite product obtained in the step (4) by using a vacuum drying oven, and drying at the temperature of 60 ℃ for 10 hours to obtain the regenerated graphite electrode material.
The regenerated graphite electrode material prepared by the method, the super conductive carbon black and the LA133 adhesive are ground and uniformly mixed according to the mass ratio of 8:1:1, deionized water is added to prepare uniform slurry, the uniform slurry is coated on an aluminum foil, the aluminum foil is dried in an oven at 80 ℃ for 10 hours, and then a pole piece with the diameter of 8mm is pressed. A 2025 button cell is assembled in a glove box in high-purity argon atmosphere by using a metal lithium sheet as a cathode (the purity of argon is more than 99.99 percent, H)2O content less than 1ppm, O2The content is less than 3 ppm). The specific capacity of the battery does not drop significantly after cycling many times.
Example 15
A regenerated graphite electrode material is prepared by a preparation method comprising the following steps:
(1) placing the waste battery in a sodium chloride solution with the mass fraction of 26.5 percent (the mass fraction of the saturated sodium chloride solution at room temperature is 26.5 percent) for discharging for 8 hours, then drying the waste battery for the first time, placing the waste battery in a drying oven with the temperature of 50 ℃ for drying for 12 hours, and then using ceramic scissors for disassembling;
(2) at 5% H2Heating the graphite cathode to 600 ℃ at the heating rate of 10 ℃/min in the atmosphere of the/Ar mixed gas, keeping the temperature for 2 hours, and then stripping graphite from a current collector to obtain waste stoneInk, in powder form;
(3) mixing 1mol/L nitric acid and the waste graphite obtained in the step (2) according to a solid-to-liquid ratio of 1g/L, stirring for 0.6h on a magneton stirrer at a rotating speed of 450rpm, and reacting to obtain a reaction liquid which is a suspension;
(4) after the reaction is finished, paving medium-speed filter paper with the diameter of 80mm on a Buchner funnel, performing vacuum filtration on the suspension obtained in the step (3), and washing with deionized water until the pH value of the filtrate is 7 to obtain a treated crude graphite product;
(5) and (4) carrying out secondary drying on the crude graphite product obtained in the step (4) by using a vacuum drying oven, and drying at the temperature of 100 ℃ for 6 hours to obtain the regenerated graphite electrode material.
The regenerated graphite electrode material prepared by the method, the super conductive carbon black and the LA133 adhesive are ground and uniformly mixed according to the mass ratio of 8:1:1, deionized water is added to prepare uniform slurry, the uniform slurry is coated on an aluminum foil, the aluminum foil is dried in an oven at 80 ℃ for 10 hours, and then a pole piece with the diameter of 8mm is pressed. A 2025 button cell is assembled in a glove box in high-purity argon atmosphere by using a metal lithium sheet as a cathode (the purity of argon is more than 99.99 percent, H)2O content less than 1ppm, O2The content is less than 3 ppm). The specific capacity of the battery does not drop significantly after cycling many times.
Example 16
A regenerated graphite electrode material is prepared by a preparation method comprising the following steps:
(1) placing the waste batteries in a sodium chloride solution with the mass fraction of 7.8% to discharge for 12h, then drying the waste batteries for the first time, placing the batteries in a 70 ℃ drying oven to dry for 8h, and then using ceramic scissors to disassemble;
(2) heating the graphite cathode to 400 ℃ at the heating rate of 1 ℃/min in the nitrogen atmosphere, keeping the temperature for 4 hours, and then stripping graphite from a current collector to obtain waste graphite in powder form;
(3) mixing 1mol/L N, N-dimethylformamide with the waste graphite obtained in the step (2) according to a solid-liquid ratio of 70g/L, and carrying out ultrasonic treatment for 2h in an ultrasonic instrument with the power of 50W to obtain a reaction solution which is a suspension;
(4) after the reaction is finished, paving medium-speed filter paper with the diameter of 80mm on a Buchner funnel, carrying out vacuum filtration on the suspension obtained in the step (3), repeating the step (3) on the obtained filter residue for three times, and carrying out vacuum filtration for 30min each time to obtain a treated crude graphite product;
(5) and (4) carrying out secondary drying on the crude graphite product obtained in the step (4) by using a vacuum drying oven, and drying at the temperature of 93 ℃ for 6.5h to obtain the regenerated graphite electrode material.
The regenerated graphite electrode material prepared by the method, the super conductive carbon black and the LA133 adhesive are ground and uniformly mixed according to the mass ratio of 8:1:1, deionized water is added to prepare uniform slurry, the uniform slurry is coated on an aluminum foil, the aluminum foil is dried in an oven at 80 ℃ for 10 hours, and then a pole piece with the diameter of 8mm is pressed. A 2025 button cell is assembled in a glove box in high-purity argon atmosphere by using a metal lithium sheet as a cathode (the purity of argon is more than 99.99 percent, H)2O content less than 1ppm, O2The content is less than 3 ppm). The specific capacity of the battery does not drop significantly after cycling many times.
Example 17
A regenerated graphite electrode material is prepared by a preparation method comprising the following steps:
(1) placing the waste batteries in a sodium chloride solution with the mass fraction of 18.2% to discharge for 12 hours, then drying the waste batteries for the first time, placing the batteries in a 70 ℃ drying oven to dry for 8 hours, and then disassembling the batteries by using ceramic scissors;
(2) heating the graphite cathode to 400 ℃ at the heating rate of 1 ℃/min in the nitrogen atmosphere, keeping the temperature for 4 hours, and then stripping graphite from a current collector to obtain waste graphite in powder form;
(3) mixing ethanol with the waste graphite obtained in the step (2) according to a solid-liquid ratio of 35g/L, and carrying out ultrasonic treatment in an ultrasonic instrument with power of 150W for 0.7h to obtain a reaction liquid, namely a suspension;
(4) after the reaction is finished, paving medium-speed filter paper with the diameter of 80mm on a Buchner funnel, carrying out vacuum filtration on the suspension obtained in the step (3), repeating the step (3) on the obtained filter residue for three times, and carrying out vacuum filtration for 30min each time to obtain a treated crude graphite product;
(5) and (4) carrying out secondary drying on the crude graphite product obtained in the step (4) by using a vacuum drying oven, and drying at the temperature of 67 ℃ for 9.4h to obtain the regenerated graphite electrode material.
The regenerated graphite electrode material prepared by the method, the super conductive carbon black and the LA133 adhesive are ground and uniformly mixed according to the mass ratio of 8:1:1, deionized water is added to prepare uniform slurry, the uniform slurry is coated on an aluminum foil, the aluminum foil is dried in an oven at 80 ℃ for 10 hours, and then a pole piece with the diameter of 8mm is pressed. A 2025 button cell is assembled in a glove box in high-purity argon atmosphere by using a metal lithium sheet as a cathode (the purity of argon is more than 99.99 percent, H)2O content less than 1ppm, O2The content is less than 3 ppm). The specific capacity of the battery does not drop significantly after cycling many times.
Example 18
A regenerated graphite electrode material is prepared by a preparation method comprising the following steps:
(1) placing the waste batteries in a sodium chloride solution with the mass fraction of 21.5% to discharge for 12h, then drying the waste batteries for the first time, placing the batteries in a 70 ℃ drying oven to dry for 8h, and then disassembling the batteries by using ceramic scissors;
(2) heating the graphite cathode to 400 ℃ at the heating rate of 1 ℃/min in the nitrogen atmosphere, keeping the temperature for 4 hours, and then stripping graphite from a current collector to obtain waste graphite in powder form;
(3) mixing deionized water with the waste graphite obtained in the step (2) according to a solid-liquid ratio of 100g/L, and carrying out ultrasonic treatment in an ultrasonic instrument with the power of 70W for 1.6h to obtain a reaction liquid, namely a suspension;
(4) after the reaction is finished, paving medium-speed filter paper with the diameter of 80mm on a Buchner funnel, carrying out vacuum filtration on the suspension obtained in the step (3), repeating the step (3) on the obtained filter residue for three times, and carrying out vacuum filtration for 30min each time to obtain a treated crude graphite product;
(5) and (4) carrying out secondary drying on the crude graphite product obtained in the step (4) by using a vacuum drying oven, and drying at the temperature of 84 ℃ for 7.8h to obtain the regenerated graphite electrode material.
The regenerated graphite electrode material prepared by the method, the super conductive carbon black and the LA133 adhesive are ground and uniformly mixed according to the mass ratio of 8:1:1, deionized water is added to prepare uniform slurry, the uniform slurry is coated on an aluminum foil, the aluminum foil is dried in an oven at 80 ℃ for 10 hours, and then a pole piece with the diameter of 8mm is pressed. A 2025 button cell is assembled in a glove box in high-purity argon atmosphere by using a metal lithium sheet as a cathode (the purity of argon is more than 99.99 percent, H)2O content less than 1ppm, O2The content is less than 3 ppm). The specific capacity of the battery does not drop significantly after cycling many times.
Comparative example 1
The general waste graphite which is not treated after circulation is prepared by the following steps:
(1) placing the waste batteries in a sodium chloride solution with the mass fraction of 5% for discharging for 10h, then drying the waste batteries for the first time, placing the batteries in a drying oven at 60 ℃ for drying for 10h, and then disassembling the batteries by using ceramic scissors;
(2) the graphite negative electrode is processed by a manual stripping method: scraping Graphite off a current collector by using a blade to obtain waste Graphite which is powdery, wherein an XRD (X-ray diffraction) diagram is shown in figure 1, the waste Graphite after multiple cycles still keeps the original layered crystal structure of the Graphite, the XRD diagram corresponds to the PDF #41-1487Graphite-2H crystal phase in a PDF card, diffraction peaks are shown in crystal planes (002), (101) and (004), but the characteristic peak positions at two positions with diffraction angles of 44.39 degrees and 54.5 degrees are slightly shifted, because intermediate products in the charge-discharge process, such as residual lithium salt and the like, are doped between electrode layers of the Graphite after the cycles, the spacing of the crystal layers is changed, and the shift of the diffraction peak positions is caused; in addition, with the continuous release and insertion of lithium ions in the charging and discharging process of the battery, intermolecular force between graphite layers is weakened, the crystal structure is loosened and distorted, and the position of a diffraction peak is also changed.
Grinding and uniformly mixing the obtained recycled waste graphite, the super conductive carbon black and the LA133 adhesive according to the mass ratio of 8:1:1, adding deionized water to prepare uniform slurry, coating the uniform slurry on an aluminum foil, and drying the aluminum foil in an oven at 80 DEG C10h, and then pressing into a pole piece with the diameter of 8 mm. A 2025 button cell is assembled in a glove box in high-purity argon atmosphere by using a metal lithium sheet as a cathode (the purity of argon is more than 99.99 percent, H)2O content less than 1ppm, O2The content is less than 3 ppm). The obtained first-turn charge-discharge curve, discharge specific capacity-cycle number curve, charge-discharge efficiency curve and multiplying power curve under different current densities are respectively shown in fig. 2, 3, 4, 5 and 6. By comparison, it can be seen that the graphite electrode of comparative example 1 was slow in discharge, low in discharge capacity, and unable to perform stable long-term charge-discharge cycles.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. The preparation method of the regenerated graphite electrode material is characterized by comprising the following steps:
(a) placing the waste battery in a salt solution for discharging, and sequentially performing primary drying, disassembly and stripping after discharging to obtain waste graphite;
(b) mixing the waste graphite obtained in the step (a) with a reaction solvent, and reacting to obtain a reaction solution;
(c) and (c) carrying out suction filtration on the reaction liquid obtained in the step (b) to obtain a crude graphite product, and carrying out secondary drying on the crude graphite product to obtain the regenerated graphite electrode material.
2. The method for preparing a regenerated graphite electrode material according to claim 1, wherein in the step (a), the salt solution is a sodium chloride solution, and the mass concentration of the sodium chloride solution is 5-26.5%.
3. The method of claim 1, wherein in the step (a), the discharging time is 8-12h, the first drying temperature is 50-70 ℃, and the first drying time is 8-12 h.
4. The method as claimed in claim 1, wherein in the step (a), the stripping is performed by manual stripping or sintering stripping, the sintering stripping temperature is 400-600 ℃, the sintering stripping time is 2-4h, and the heating rate is 1-10 ℃/min.
5. The method of claim 1, wherein in step (b), the reaction solvent is one or more selected from water, ethanol, N-dimethylformamide, sulfuric acid, hydrochloric acid, and nitric acid.
6. The method according to claim 5, wherein in the step (c), when the reaction solvent is an acidic substance, the pH of the reaction solution is adjusted to neutral during the suction filtration.
7. The method as claimed in claim 1, wherein in the step (b), ultrasonic dispersion or stirring dispersion is performed during the reaction, the ultrasonic power is 50-150W, the stirring speed is 350-450rpm, and the reaction time is 0.5-2 h.
8. The method for preparing a regenerated graphite electrode material according to claim 1, wherein in the step (c), the suction filtration is performed under vacuum condition, and the suction filtration time is 0.5-1 h;
in the step (c), the second drying is carried out under the vacuum condition, the temperature of the second drying is 60-100 ℃, and the time of the second drying is 6-10 h.
9. A regenerated graphite electrode material obtained by the production method as claimed in any one of claims 1 to 8.
10. Use of the regenerated graphite electrode material according to claim 9.
CN202010561954.5A 2020-03-20 2020-06-18 Regenerated graphite electrode material and preparation method and application thereof Pending CN111883772A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113871742A (en) * 2021-08-23 2021-12-31 中南大学 Method for recycling and reusing graphite cathode in waste battery
CN113860351A (en) * 2021-08-23 2021-12-31 中南大学 Preparation method and application of CuO-graphite composite material prepared from waste graphite

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103259062A (en) * 2013-04-17 2013-08-21 清华大学深圳研究生院 Method for regenerating graphene by recovering waste lithium ion battery
CN103370829A (en) * 2011-02-15 2013-10-23 住友化学株式会社 Method of recovering active material from scrap battery material
CN107317048A (en) * 2017-05-26 2017-11-03 金川集团股份有限公司 The method that copper foil and graphite are reclaimed from negative electrode material of waste lithium ion battery
US20180230014A1 (en) * 2015-08-11 2018-08-16 Metoxs Pte Ltd. Method for cost-efficient industrial production of graphite oxide, graphene oxide and graphene
CN110589812A (en) * 2019-09-17 2019-12-20 华南理工大学 Method for preparing porous graphene by recovering graphite cathode material from waste power battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103370829A (en) * 2011-02-15 2013-10-23 住友化学株式会社 Method of recovering active material from scrap battery material
CN103259062A (en) * 2013-04-17 2013-08-21 清华大学深圳研究生院 Method for regenerating graphene by recovering waste lithium ion battery
US20180230014A1 (en) * 2015-08-11 2018-08-16 Metoxs Pte Ltd. Method for cost-efficient industrial production of graphite oxide, graphene oxide and graphene
CN107317048A (en) * 2017-05-26 2017-11-03 金川集团股份有限公司 The method that copper foil and graphite are reclaimed from negative electrode material of waste lithium ion battery
CN110589812A (en) * 2019-09-17 2019-12-20 华南理工大学 Method for preparing porous graphene by recovering graphite cathode material from waste power battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113871742A (en) * 2021-08-23 2021-12-31 中南大学 Method for recycling and reusing graphite cathode in waste battery
CN113860351A (en) * 2021-08-23 2021-12-31 中南大学 Preparation method and application of CuO-graphite composite material prepared from waste graphite

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