CN107706478B - Recovery method of battery capacitor - Google Patents

Recovery method of battery capacitor Download PDF

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CN107706478B
CN107706478B CN201710950899.7A CN201710950899A CN107706478B CN 107706478 B CN107706478 B CN 107706478B CN 201710950899 A CN201710950899 A CN 201710950899A CN 107706478 B CN107706478 B CN 107706478B
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battery
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pole piece
mixed powder
battery capacitor
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CN107706478A (en
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阮殿波
吴奕环
郑超
陈雪丹
于学文
刘秋香
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Ningbo CRRC New Energy Technology Co Ltd
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Ningbo CSR New Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention belongs to the technical field of battery recovery, and particularly relates to a recovery method of a battery capacitor. The method comprises the steps of pretreatment, chemical treatment, modification and repair and the like, and the invalid hybrid battery capacitor is recycled and reused. Different from the traditional battery recycling method which focuses on recycling materials, the method disclosed by the invention has the advantages that the recycled invalid materials are modified and repaired, so that the invalid materials can be assembled into the battery capacitor again, the loss and waste of resources can be greatly reduced, the cyclic regeneration of the battery capacitor is achieved, and the good benefit of large-scale recycling is achieved. Meanwhile, the whole operation process is carried out in a totally-enclosed environment, and the method is green and environment-friendly. The limitation of the traditional digital lithium battery recovery method is changed, the invalid hybrid battery capacitor can be recycled, and the application range is wider.

Description

Recovery method of battery capacitor
Technical Field
The invention belongs to the technical field of battery recovery, and particularly relates to a recovery method of a battery capacitor.
Background
Lithium batteries are widely used in modern electronic devices due to their high energy density, light weight, long life and no memory effect. With the high-speed development of economy and the trend of miniaturization of electric appliances, the development prospect is wide. Energy exhaustion and environmental pollution have become problems that the current society has to face and urgently need to solve, and thus electric vehicles and hybrid electric vehicles are gaining increasing attention from more and more countries.
With the recent years, new energy automobiles are gradually paid attention to and popularized and become a necessary trend for replacing traditional automobiles, and the output of lithium batteries is rapidly increased as a power source of the new energy automobiles. In recent years, the output of new energy automobiles is estimated to reach millions of vehicles, and the demand of dozens of thousands of tons of lithium batteries is driven. The service life of the automobile lithium battery is generally 3-8 years, and the important research is how to recycle the lithium battery after the lithium battery is discarded.
In the prior art, materials of all parts of a waste battery are generally recycled respectively to increase the recycling rate. At present, waste digital lithium ionsThe recycling process of batteries has been developed to a great extent, and its main material is LiC 002However, the method is not suitable for hybrid battery capacitors, and the recycling research on the positive and negative electrode materials of waste lithium batteries is relatively few.
Aiming at the defects of insufficient recovery, low utilization rate and the like of the existing battery materials, publication No. 102664294A discloses a recovery method of waste lithium iron phosphate batteries, which improves the recovery utilization rate of metal elements and the like in the batteries. However, a method for recovering a certain battery is only applied to a narrow range of applications and cannot be widely popularized, and the battery cannot be regenerated simply by classifying and recovering the battery raw materials.
Disclosure of Invention
Aiming at the problems, the invention provides a high-utilization and environment-friendly method for recycling the failed hybrid battery capacitor and a method for preparing the battery capacitor by using recycled materials.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of recycling battery capacitance, the method comprising the steps of:
(1) pretreatment: carrying out complete discharge treatment on the battery capacitor, cutting the package, taking out the battery core, disassembling the battery core, and sorting out a positive pole piece and a negative pole piece;
(2) chemical treatment: the pole piece is sequentially soaked in a dimethyl carbonate solution and 1-methyl-2-pyrrolidone, ultrasonic oscillation is carried out while stirring is carried out while the pole piece is soaked in the 1-methyl-2-pyrrolidone, and then a current collector, a diaphragm and mixed powder are separated by filtration;
(3) modification and repair: and washing the mixed powder, drying, performing ball milling treatment, sieving to obtain mixed powder, and finally performing heat treatment to obtain the electrode active material of the battery capacitor.
In the current battery recycling method, the batteries are decomposed into metal raw materials to be recycled, melted, refined and reused, and most of the recycled batteries are digital lithium ion batteries, and the main material of the recycled batteries is LiC 002But are not suitable for mixingA battery capacitor. The invention develops a recycling method according to the increasing mixed battery capacitors on the market and the future recycling situation, and can be reassembled into the battery after being modified and repaired by using the recycled anode and cathode materials, so that the loss and waste of resources can be greatly reduced, the recycling of the battery is realized, and the good benefit of large-scale recycling is achieved. Meanwhile, the whole set of recovery process is carried out in a closed workshop, and the generated waste gas can be purified, so that the problem of environmental pollution caused by recovery is avoided. The invention can realize green, high-efficiency and pollution-free recovery of the hybrid battery capacitor.
Preferably, in the battery capacitor recycling method, ceramic scissors are used for cutting the package in the pretreatment. Although the waste battery capacitor is subjected to complete discharge treatment, the operation safety needs to be kept careful at any time, and the ceramic scissors can effectively prevent the damage caused by residual electricity which may be left.
Preferably, in the method for recovering the battery capacitor, the soaking time of the dimethyl carbonate solution in the chemical treatment is 3-4h, and the temperature is normal temperature. Electrolyte with different contents usually exists in the failed battery capacitor pole piece, the activity of the residual electrolyte is lost, the dimethyl carbonate can be fully mixed with the electrolyte to achieve the effect of removing the electrolyte, and meanwhile, the dimethyl carbonate is a material with low toxicity and excellent environmental protection performance and meets the requirement of green chemistry.
Preferably, in the method for recovering the battery capacitor, the soaking time of the 1-methyl-2-pyrrolidone in the chemical treatment is 6-8h, and the temperature is 65-85 ℃. NMP is a polar aprotic solvent, and has the advantages of low toxicity, high boiling point, excellent dissolving power, strong selectivity and good stability. At 65-85 ℃, NMP has extremely high intermiscibility with the adhesive in the pole piece, and the adhesive in the failed pole piece can be removed to the maximum extent. Meanwhile, when the temperature is too low, the compatibility of the binding agent in the pole piece and NMP is poor, and when the temperature is too high, the solvent is easy to volatilize.
Preferably, in the method for recovering battery capacity, the ultrasonic oscillation in the chemical treatment is specifically: firstly, the frequency is adjusted to be 30-33KHz and kept for 1-2h, then the frequency is increased to 38-40KHz at the speed of 2-3KHz/h and kept for 0.1-0.3h, and finally the frequency is reduced to 33-35KHz at the speed of 3-4KHz/h and kept for 0.3-0.5 h. The stepped change in ultrasonic frequency facilitates full separation of the portions of the pole piece. The ultrasonic wave with lower frequency can reduce the binding force among all parts of the pole piece at the beginning, and all parts of the pole piece can be slowly separated along with the increase of the ultrasonic frequency, so that the loss of active substances in the pole piece caused by rapid separation is avoided, and finally, the ultrasonic frequency is gradually reduced to be beneficial to the separation of the active substances.
Preferably, in the battery capacitor recovery method, after filtration in chemical treatment, the active materials in the pole pieces are separated from the current collector respectively, an aluminum foil, a copper foil and a diaphragm are obtained on a screen, and mixed powder is obtained under the screen.
Preferably, in the method for recovering the battery capacitor, the washing reagent in the modification repair is one or two of absolute ethyl alcohol and acetone, the washing time of the reagent is 3-5min, the drying is in a vacuum environment, the drying temperature is 60-80 ℃, and the drying time is 10-15 h. The reagent can remove impurities in the material, can take away moisture, and can effectively prevent the material from being oxidized by oxygen in the air to permanently lose efficacy by drying under the vacuum condition.
Preferably, in the method for recovering the battery capacitor, the ball milling rotation speed in the modification repair is 300-500r/min, and the ball milling time is 1-3 h. The full ball milling can reduce the particle size of the material, increase the specific surface area of the material and fully exert the discharge effect of the battery.
Preferably, in the method for recovering battery capacity, the heat treatment specifically includes: firstly storing the ball-milled mixed powder for 1-3h at the low temperature of 0-2 ℃, then placing the mixed powder in a vacuum environment, heating to 600-650 ℃ at the speed of 10-30 ℃/min, keeping for 6-8h, heating to 750-800 ℃ at the speed of 40-60 ℃/min, keeping for 2-4h, and finally naturally cooling to the room temperature to obtain the electrode active material. The low-temperature storage can avoid loss caused by the combination of mixed powder and trace impurities, the gradient temperature rise can enable the active material to adapt to the external temperature change, and the permanent inactivation of substances caused by rapid temperature rise is avoided. The heat treatment can restore the discharge activity of the failed material and regenerate the failed material.
Compared with the prior art, the invention has the following advantages:
(1) the limitation of the traditional digital lithium battery recovery method is changed, the invalid hybrid battery capacitor can be recycled, and the application range is wider.
(2) The invention can realize green, friendly and pollution-free recovery of waste battery capacitors.
(3) The invention can utilize the material of the waste battery capacitor to directly assemble a new battery after modification and repair while recycling the waste battery capacitor.
(4) The invention has low recycling cost and good benefit.
Drawings
Fig. 1 is a graph of rate capability of the electrode active material of the present invention.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Example 1
Pretreatment: and (3) carrying out complete discharge treatment on the recovered failure battery capacitor, cutting the package with ceramic scissors to take out the battery core, and then separating out the positive pole piece and the negative pole piece after disassembling the battery core.
Chemical treatment: the pole piece is soaked in dimethyl carbonate solution for 3.5h at normal temperature. Taking out and evaporating dimethyl carbonate to dryness, then putting the dimethyl carbonate into 1-methyl-2-pyrrolidone for soaking, setting the temperature to be 75 ℃, simultaneously stirring and carrying out ultrasonic oscillation, firstly adjusting the ultrasonic frequency to be 32KHz, keeping the ultrasonic frequency for 1.5h, then increasing the frequency to 39KHz at the speed of 2.5KHz/h, keeping the ultrasonic frequency for 0.2h, and finally reducing the frequency to 34KHz at the speed of 3.5KHz/h, and keeping the ultrasonic frequency for 0.4 h. And after filtering, respectively separating the active material in the pole piece from the current collector, and obtaining an aluminum foil, a copper foil and a diaphragm on the screen and mixed powder under the screen.
Modification and repair: washing the mixed powder with anhydrous ethanol for 4min, volatilizing the anhydrous ethanol after washing, placing the mixed powder in a vacuum environment, setting the drying temperature at 70 ℃, and drying for 12 h. And performing ball milling treatment on the dried mixed powder, setting the ball milling rotation speed to be 400r/min, and performing ball milling for 2 hours to obtain mixed powder. And storing the ball-milled mixed powder for 2h at the low temperature of 1 ℃, then placing the mixed powder in a vacuum environment, heating to 350 ℃ at the speed of 20 ℃/min, keeping for 3h, heating to 600 ℃ at the speed of 25 ℃/min, keeping for 7h, and finally naturally cooling to room temperature to obtain the electrode active material.
Processing of active materials: dissolving polyvinylidene fluoride powder in N-methyl pyrrolidone to form a mixed solution, mixing the electrode active material prepared in the embodiment with carbon black, adding the mixture into the mixed solution, and stirring to obtain slurry.
Forming a pole piece: coating the slurry on an aluminum foil by using an automatic coating machine, evaporating the N-methyl pyrrolidone to dryness at 70 ℃ under normal pressure, and drying in vacuum at the drying temperature of 120 ℃ for 12 hours. And finally, rolling, slicing and weighing to obtain the pole piece.
Assembling a finished product: assembling the positive pole piece and the negative pole piece into a finished product of the battery capacitor in a glove box filled with argon, wherein the assembling electrolyte is 1mol/L LiPF6+EC/DEC+DMC(Vol 1:1:1)。
Example 2
Pretreatment: and (3) carrying out complete discharge treatment on the recovered failure battery capacitor, cutting the package with ceramic scissors to take out the battery core, and then separating out the positive pole piece and the negative pole piece after disassembling the battery core.
Chemical treatment: the pole piece is soaked in dimethyl carbonate solution for 3.5h at normal temperature. Taking out and evaporating dimethyl carbonate to dryness, then putting the dimethyl carbonate into 1-methyl-2-pyrrolidone for soaking, setting the temperature to be 75 ℃, simultaneously stirring and carrying out ultrasonic oscillation, firstly adjusting the ultrasonic frequency to be 32KHz, keeping the ultrasonic frequency for 1.5h, then increasing the frequency to 39KHz at the speed of 2.5KHz/h, keeping the ultrasonic frequency for 0.2h, and finally reducing the frequency to 34KHz at the speed of 3.5KHz/h, and keeping the ultrasonic frequency for 0.4 h. And after filtering, respectively separating the active material in the pole piece from the current collector, and obtaining an aluminum foil, a copper foil and a diaphragm on the screen and mixed powder under the screen.
Modification and repair: washing the mixed powder with anhydrous ethanol for 4min, volatilizing the anhydrous ethanol after washing, placing the mixed powder in a vacuum environment, setting the drying temperature at 70 ℃, and drying for 12 h. And performing ball milling treatment on the dried mixed powder, setting the ball milling rotation speed to be 400r/min, and performing ball milling for 2 hours to obtain mixed powder. And storing the ball-milled mixed powder for 2h at the low temperature of 1 ℃, then placing the mixed powder in a vacuum environment, heating to 350 ℃ at the speed of 20 ℃/min, keeping for 3h, heating to 650 ℃ at the speed of 25 ℃/min, keeping for 7h, and finally naturally cooling to room temperature to obtain the electrode active material.
Processing of active materials: dissolving polyvinylidene fluoride powder in N-methyl pyrrolidone to form a mixed solution, mixing the electrode active material prepared in the embodiment with carbon black, adding the mixture into the mixed solution, and stirring to obtain slurry.
Forming a pole piece: coating the slurry on an aluminum foil by using an automatic coating machine, evaporating the N-methyl pyrrolidone to dryness at 70 ℃ under normal pressure, and drying in vacuum at the drying temperature of 120 ℃ for 12 hours. And finally, rolling, slicing and weighing to obtain the pole piece.
Assembling a finished product: assembling the positive pole piece and the negative pole piece into a finished product of the battery capacitor in a glove box filled with argon, wherein the assembling electrolyte is 1mol/L LiPF6+EC/DEC+DMC(Vol 1:1:1)。
Example 3
Pretreatment: and (3) carrying out complete discharge treatment on the recovered failure battery capacitor, cutting the package with ceramic scissors to take out the battery core, and then separating out the positive pole piece and the negative pole piece after disassembling the battery core.
Chemical treatment: the pole piece is soaked in dimethyl carbonate solution for 3.5h at normal temperature. Taking out and evaporating dimethyl carbonate to dryness, then putting the dimethyl carbonate into 1-methyl-2-pyrrolidone for soaking, setting the temperature to be 75 ℃, simultaneously stirring and carrying out ultrasonic oscillation, firstly adjusting the ultrasonic frequency to be 32KHz, keeping the ultrasonic frequency for 1.5h, then increasing the frequency to 39KHz at the speed of 2.5KHz/h, keeping the ultrasonic frequency for 0.2h, and finally reducing the frequency to 34KHz at the speed of 3.5KHz/h, and keeping the ultrasonic frequency for 0.4 h. And after filtering, respectively separating the active material in the pole piece from the current collector, and obtaining an aluminum foil, a copper foil and a diaphragm on the screen and mixed powder under the screen.
Modification and repair: washing the mixed powder with anhydrous ethanol for 4min, volatilizing the anhydrous ethanol after washing, placing the mixed powder in a vacuum environment, setting the drying temperature at 70 ℃, and drying for 12 h. And performing ball milling treatment on the dried mixed powder, setting the ball milling rotation speed to be 400r/min, and performing ball milling for 2 hours to obtain mixed powder. And storing the ball-milled mixed powder for 2h at the low temperature of 1 ℃, then placing the mixed powder in a vacuum environment, heating to 350 ℃ at the speed of 20 ℃/min, keeping for 3h, heating to 700 ℃ at the speed of 25 ℃/min, keeping for 7h, and finally naturally cooling to room temperature to obtain the electrode active material.
Processing of active materials: dissolving polyvinylidene fluoride powder in N-methyl pyrrolidone to form a mixed solution, mixing the electrode active material prepared in the embodiment with carbon black, adding the mixture into the mixed solution, and stirring to obtain slurry.
Forming a pole piece: coating the slurry on an aluminum foil by using an automatic coating machine, evaporating the N-methyl pyrrolidone to dryness at 70 ℃ under normal pressure, and drying in vacuum at the drying temperature of 120 ℃ for 12 hours. And finally, rolling, slicing and weighing to obtain the pole piece.
Assembling a finished product: assembling the positive pole piece and the negative pole piece into a finished product of the battery capacitor in a glove box filled with argon, wherein the assembling electrolyte is 1mol/L LiPF6+EC/DEC+DMC(Vol 1:1:1)。
Example 4
Pretreatment: and (3) carrying out complete discharge treatment on the recovered failure battery capacitor, cutting the package with ceramic scissors to take out the battery core, and then separating out the positive pole piece and the negative pole piece after disassembling the battery core.
Chemical treatment: the pole piece is soaked in dimethyl carbonate solution for 3h at normal temperature. Taking out and evaporating dimethyl carbonate to dryness, then putting the dimethyl carbonate into 1-methyl-2-pyrrolidone for soaking, setting the temperature to be 65 ℃, simultaneously stirring and carrying out ultrasonic oscillation, firstly adjusting the ultrasonic frequency to be 30KHz, keeping for 1h, then increasing the frequency to 38KHz at the speed of 2KHz/h, keeping for 0.1h, finally reducing the frequency to 33KHz at the speed of 3KHz/h, and keeping for 0.3 h. And after filtering, respectively separating the active material in the pole piece from the current collector, and obtaining an aluminum foil, a copper foil and a diaphragm on the screen and mixed powder under the screen.
Modification and repair: washing the mixed powder with anhydrous ethanol for 3min, volatilizing the anhydrous ethanol after washing, placing the mixed powder in a vacuum environment, setting the drying temperature at 60 ℃, and drying for 10 h. And performing ball milling treatment on the dried mixed powder, setting the ball milling rotation speed to 300r/min, and performing ball milling for 1h to obtain mixed powder. And storing the ball-milled mixed powder for 1h at the low temperature of 0 ℃, then placing the mixed powder in a vacuum environment, heating to 300 ℃ at the speed of 10 ℃/min, keeping for 2h, heating to 600 ℃ at the speed of 15 ℃/min, keeping for 6h, and finally naturally cooling to room temperature to obtain the electrode active material.
Processing of active materials: dissolving polyvinylidene fluoride powder in N-methyl pyrrolidone to form a mixed solution, mixing the electrode active material prepared in the embodiment with carbon black, adding the mixture into the mixed solution, and stirring to obtain slurry.
Forming a pole piece: coating the slurry on an aluminum foil by using an automatic coating machine, evaporating the N-methyl pyrrolidone to dryness at 60 ℃ under normal pressure, and drying in vacuum at the drying temperature of 100 ℃ for 10 hours. And finally, rolling, slicing and weighing to obtain the pole piece.
Assembling a finished product: assembling the positive pole piece and the negative pole piece into a finished product of the battery capacitor in a glove box filled with argon, wherein the assembling electrolyte is 1mol/L LiPF6+EC/DEC+DMC(Vol 1:1:1)。
Example 5
Pretreatment: and (3) carrying out complete discharge treatment on the recovered failure battery capacitor, cutting the package with ceramic scissors to take out the battery core, and then separating out the positive pole piece and the negative pole piece after disassembling the battery core.
Chemical treatment: the pole piece is soaked in dimethyl carbonate solution for 4 hours at normal temperature. Taking out and evaporating dimethyl carbonate to dryness, then putting the dimethyl carbonate into 1-methyl-2-pyrrolidone for soaking, setting the temperature to be 85 ℃, simultaneously stirring and carrying out ultrasonic oscillation, firstly adjusting the ultrasonic frequency to be 33KHz, keeping for 2 hours, then increasing the frequency to 40KHz at the speed of 3KHz/h, keeping for 0.3 hours, finally reducing the frequency to 35KHz at the speed of 4KHz/h, and keeping for 0.5 hours. And after filtering, respectively separating the active material in the pole piece from the current collector, and obtaining an aluminum foil, a copper foil and a diaphragm on the screen and mixed powder under the screen.
Modification and repair: washing the mixed powder with anhydrous ethanol for 5min, volatilizing the anhydrous ethanol after washing, placing the mixed powder in a vacuum environment, setting the drying temperature at 80 ℃, and drying for 15 h. And performing ball milling treatment on the dried mixed powder, setting the ball milling rotation speed to be 500r/min, and performing ball milling for 3 hours to obtain mixed powder. And storing the ball-milled mixed powder for 3h at the low temperature of 2 ℃, then placing the mixed powder in a vacuum environment, heating to 400 ℃ at the speed of 30 ℃/min, keeping for 4h, heating to 600 ℃ at the speed of 35 ℃/min, keeping for 8h, and finally naturally cooling to room temperature to obtain the electrode active material.
Processing of active materials: dissolving polyvinylidene fluoride powder in N-methyl pyrrolidone to form a mixed solution, mixing the electrode active material prepared in the embodiment with carbon black, adding the mixture into the mixed solution, and stirring to obtain slurry.
Forming a pole piece: coating the slurry on an aluminum foil by using an automatic coating machine, evaporating the N-methyl pyrrolidone to dryness at 80 ℃ under normal pressure, and drying in vacuum at the drying temperature of 150 ℃ for 15 hours. And finally, rolling, slicing and weighing to obtain the pole piece.
Assembling a finished product: assembling the positive pole piece and the negative pole piece into a finished product of the battery capacitor in a glove box filled with argon, wherein the assembling electrolyte is 1mol/L LiPF6+EC/DEC+DMC(Vol 1:1:1)。
Example 6
The only difference from example 2 is that the specific experimental object of example 6 is only the positive electrode plate of the battery capacitor.
Example 7
The only difference from example 2 is that the specific experimental object of example 7 is only the negative electrode sheet of the battery capacitor.
Comparative example 1
The only difference from example 2 is that the final temperature increase to 750 ℃ in the modified repair of comparative example 1.
Comparative example 2
The only difference from example 2 is that the final temperature increase to 800 ℃ in the modified repair of comparative example 2.
Comparative example 3
The only difference from example 2 is that the final temperature increase to 500 ℃ in comparative example 3 modified repair.
The finished battery capacitors obtained in examples 1 to 7 and comparative examples 1 to 3 were tested for rate capability, and the results are shown in table 1:
table 1: rate capability of electrode active materials in examples 1 to 7 and comparative examples 1 to 3
Figure BDA0001432832770000101
Wherein, the data under the last group of 0.2C in the table 1 is the performance data of the product which can return to the original 0.2C after being charged and discharged by 0.2C and 1-5C large electric quantity.
The results of the tests on the products of examples 1-3 and comparative examples 1-2 are plotted in FIG. 1, under the following test conditions: charging and discharging at a charging rate of 0.2C (wherein 1C is 150mA/g) and a voltage range of 2.5-4.2V, and circulating for 30 weeks; charging and discharging the mixture at a charging multiplying power of l-5C and a voltage range of 2.0-4.2V, and circulating for 10 weeks. As can be seen from the figure, the heat treatment temperature is increased from 600 ℃ to 650 ℃, the specific discharge capacity is greatly improved, and the sample of the example 2 has very high specific discharge capacity compared with the untreated sample at 0.2 ℃; at 5C, the example 2 sample has very good specific discharge capacity (second to no use) and good rate performance compared to the unused sample. Example 1 the polarization phenomenon of the sample still existed, the polarization phenomenon had disappeared completely when the heat treatment temperature was increased from 650 c to 700 c, and the polarization phenomenon reappeared when the heat treatment temperature was increased to 800 c, and it is likely that the active material had already started to decompose. Therefore, the high-temperature heat treatment can eliminate the polarization phenomenon, improve the rate capability and have better performance at the temperature of 600-700 ℃.
Meanwhile, in examples 6 to 7, only the positive electrode or the negative electrode of the battery capacitor was collected, but the actual recovery time was almost the same as that in example 1, and it is considered that the actual recovery processing environments of the positive electrode and the negative electrode were the same in the recovery of the battery capacitor, and the recovery efficiency was improved by the collective processing.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims (5)

1. A method of recycling battery capacitance, the method comprising the steps of:
(1) pretreatment: carrying out complete discharge treatment on the battery capacitor, cutting the package, taking out the battery core, disassembling the battery core, and sorting out a positive pole piece and a negative pole piece;
(2) chemical treatment: the pole piece is sequentially soaked in a dimethyl carbonate solution and 1-methyl-2-pyrrolidone, ultrasonic oscillation is carried out while stirring is carried out while the pole piece is soaked in the 1-methyl-2-pyrrolidone, and then a current collector, a diaphragm and mixed powder are separated by filtration;
(3) modification and repair: washing the mixed powder, drying, performing ball milling treatment, sieving to obtain mixed powder, and finally performing heat treatment to obtain an electrode active material of the battery capacitor;
in the modification repair, a washing reagent is one or two of absolute ethyl alcohol and acetone, the washing time is 3-5min, the drying is a vacuum environment, the drying temperature is 60-80 ℃, and the drying time is 10-15 h; the heat treatment specifically comprises the following steps: firstly storing the ball-milled mixed powder for 1-3h at the low temperature of 0-2 ℃, then placing the mixed powder in a vacuum environment, heating to 400 ℃ at the temperature of 300-30 ℃/min, keeping for 2-4h, heating to 700 ℃ at the temperature of 600-20 ℃/min, keeping for 6-8h, and finally naturally cooling to the room temperature to obtain the electrode active material.
2. The method of claim 1, wherein the soaking time of the dimethyl carbonate solution in the chemical treatment is 3-4h, and the temperature is normal temperature.
3. The method of claim 1, wherein the 1-methyl-2-pyrrolidone is soaked for 6-8 hours at a temperature of 65-85 ℃.
4. The method for recycling battery capacitance according to claim 1, wherein the ultrasonic oscillation is specifically: firstly, the frequency is adjusted to be 30-33KHz and kept for 1-2h, then the frequency is increased to 38-40KHz at the speed of 2-3KHz/h and kept for 0.1-0.3h, and finally the frequency is reduced to 33-35KHz at the speed of 3-4KHz/h and kept for 0.3-0.5 h.
5. The method as claimed in claim 1, wherein the ball milling speed is 300-500r/min and the ball milling time is 1-3 h.
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