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CN111403840A - Nondestructive disassembly method for retired power lithium battery negative plate - Google Patents

Nondestructive disassembly method for retired power lithium battery negative plate Download PDF

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Publication number
CN111403840A
CN111403840A CN201911342224.XA CN201911342224A CN111403840A CN 111403840 A CN111403840 A CN 111403840A CN 201911342224 A CN201911342224 A CN 201911342224A CN 111403840 A CN111403840 A CN 111403840A
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pole piece
lithium battery
power lithium
negative plate
freezing
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CN201911342224.XA
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CN111403840B (en
Inventor
高月春
毛信长
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Yuyao Xinhe Battery Materials Co ltd
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Yuyao Xinhe Battery Materials Co ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/54Reclaiming serviceable parts of waste accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/84Recycling of batteries or fuel cells

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Primary Cells (AREA)
  • Secondary Cells (AREA)

Abstract

The invention relates to the field of waste battery recovery, in particular to a nondestructive disassembly method for a retired power lithium battery negative plate. The method comprises the following steps: the method comprises the following steps of performing initial disassembly on a retired power lithium battery to obtain a pole piece/diaphragm composition, sequentially performing one-stage freezing, one-stage heating, two-stage freezing, two-stage heating and three-stage freezing treatment on the pole piece/diaphragm composition, placing the pole piece/diaphragm composition in an organic solvent for ultrasonic treatment after treatment, separating a pole piece from a diaphragm, and performing nondestructive disassembly to obtain a negative pole piece. The whole method is simple and efficient; the nondestructive separation and disassembly of the negative plate can be realized; the residual impurity content on the surface of the negative plate is low, and the negative plate can be directly used for preparing a new battery.

Description

Nondestructive disassembly method for retired power lithium battery negative plate
Technical Field
The invention relates to the field of waste battery recovery, in particular to a nondestructive disassembly method for a retired power lithium battery negative plate.
Background
The power lithium battery is a novel high-energy battery successfully developed in the 20 th century, is put into practical use in the 70 th year, has the advantages of high energy, high battery voltage, wide working temperature range, long storage life and the like, and is widely applied to military and civil small-sized electrical appliances, such as mobile phones, portable computers, video cameras, cameras and the like, and partially replaces the traditional battery. The high-capacity lithium battery has been tried in electric automobiles, will become one of the main power sources of the electric automobiles in the 21 st century, and will be applied to the aspects of artificial satellites, aerospace and energy storage.
The power lithium battery adopts a spiral winding structure inside, and is formed by spacing a polyethylene film isolation material with very fine and strong permeability between a positive electrode and a negative electrode. The positive electrode includes a lithium collector composed of lithium and cobalt dioxide and a current collector composed of an aluminum thin film. The negative electrode consists of a lithium collector composed of a sheet-like carbon material and a current collector composed of a copper thin film.
And as time goes on, a large number of old power lithium batteries are retired, and the old power lithium batteries are not effectively treated in the early years, so that a large number of resource waste and environmental pollution problems are caused. In recent years, with vigorous advocation and development, the heat recovery tide for retired power lithium batteries is gradually increased.
However, the current recovery is simple and rough. Because positive and negative pole pieces and diaphragm bond together in most retired power lithium cell to the negative pole produces the damage easily at disassembling the in-process, and harmless disassembling needs the manual work to operate, and is inefficient, consequently all adopt the separation mode of mixed breakage or violence disassembling to realize the separation of negative pole piece in current recovery, the negative pole piece of gained is damaged, can't continue practicality, in fact if the negative pole piece does not produce the damage, it can drop into operation again through simple surface treatment, can save the cost of manufacture of power lithium cell by very big degree, and the maximize utilization of resource has been realized. Therefore, the method for non-destructive disassembly of the negative plate has great value.
The invention patent of the method and the device for safely recycling the lithium ion battery cathode, which are disclosed by the Chinese patent office in 2017, 7 and 7 days, is typically granted by the existing cathode plate recycling operation, and the granted publication number is CN104134830B, which only reasonably and effectively utilizes the components of the cathode plate and cannot realize the nondestructive disassembly of the cathode plate.
Disclosure of Invention
The invention provides a nondestructive disassembly method for a retired power lithium battery negative plate, which aims to solve the problems that in the prior art, nondestructive disassembly of the retired power lithium battery negative plate cannot be realized, the negative plate obtained by a conventional disassembly mode is damaged more or less, the manual nondestructive disassembly efficiency of the retired power lithium battery negative plate is low, and the like. The invention aims to: firstly, nondestructive disassembly of a retired power lithium battery negative plate is realized; secondly, ensuring higher disassembling efficiency; and thirdly, reducing residual impurities on the surface of the cathode plate obtained by disassembling.
In order to achieve the purpose, the invention adopts the following technical scheme.
A nondestructive disassembly method of a retired power lithium battery negative plate,
the method comprises the following steps:
the method comprises the following steps of performing initial disassembly on a retired power lithium battery to obtain a pole piece/diaphragm composition, sequentially performing one-stage freezing, one-stage heating, two-stage freezing, two-stage heating and three-stage freezing treatment on the pole piece/diaphragm composition, placing the pole piece/diaphragm composition in an organic solvent for ultrasonic treatment after treatment, separating a pole piece from a diaphragm, and performing nondestructive disassembly to obtain a negative pole piece.
In the method, firstly, expansion/contraction difference is generated between the pole pieces (the positive pole piece and the negative pole piece) and the diaphragm through multi-section cold and hot treatment, primary separation is generated due to the contraction and expansion difference in the multiple freezing and heating processes, and the SEI film on the surface of the negative pole piece is cracked in the process, so that the bonding strength of the SEI film and the negative pole piece is reduced, and the subsequent removal of the SEI film is facilitated. After the cold-hot treatment, further ultrasonic treatment was performed. According to the invention, technical personnel originally look for a mode of searching the resonance frequency of the diaphragm to realize the complete separation of the positive plate, the negative plate and the diaphragm and improve the separation efficiency, but a great deal of research finds that the mode has poor applicability, needs to be adjusted and tested for different types of retired power lithium batteries, and the resonance is easy to cause the damage of the plates, so that the mode of ultrasonic treatment is selected for treatment. After cold and hot processing, the pole piece/diaphragm composition generates hard brittleness, the positive pole piece, the negative pole piece and the diaphragm are separated from each other in the ultrasonic processing process, and the SEI film hardened and cracked on the surface of the negative pole piece can be further removed by selecting proper ultrasonic frequency, so that the separator has a good separation and impurity removal effect.
As a preference, the first and second liquid crystal compositions are,
the preliminary disassembly process comprises removing the casing, the gasket and the sealing plate of the retired power lithium battery.
And the primary disassembly process is a conventional disassembly step, and the rest parts except the pole piece and the diaphragm in the retired power lithium battery are disassembled.
As a preference, the first and second liquid crystal compositions are,
the first-stage freezing comprises the following steps: freezing the mixture at 0-4 ℃ and 0.2-0.25 atm for 22-26 h.
In the one-stage freezing process, residual liquid impurities in the pole piece/diaphragm composition can be effectively removed, and the impurities which are fixed and difficult to remove are prevented from being formed in the subsequent heating process. And moreover, one-stage freezing adopts longer freezing time, so that the pole piece and the diaphragm can be obviously contracted and hardened while the liquid impurities are fully removed.
As a preference, the first and second liquid crystal compositions are,
the first-stage heating comprises the following steps: heating to 90-100 ℃ at a heating rate of 5-10 ℃/min, and preserving the heat for 20-30 min.
The temperature rise rate is high, and the pole piece and the diaphragm generate thermal expansion of different degrees after the temperature rise is performed quickly.
As a preference, the first and second liquid crystal compositions are,
the two-stage freezing comprises the following steps: freezing for 20-30 min at-8 to-5 ℃.
After the secondary freezing treatment, the pole piece and the diaphragm contract again, so that the bonding strength of the pole piece and the diaphragm is reduced under the condition of cold contraction.
As a preference, the first and second liquid crystal compositions are,
the two-stage heating comprises the following steps: heating to 130-150 ℃ at a heating rate of 5-10 ℃/min, and preserving the heat for 20-30 min.
The higher heating temperature is adopted in the two-stage heating, so that the expansion difference between the pole piece and the diaphragm is more obvious.
As a preference, the first and second liquid crystal compositions are,
the three-stage freezing is as follows: freezing for 30-35 min at-20 to-18 ℃.
And the shrinkage is carried out at lower temperature, so that the pole piece and the diaphragm can be basically separated preliminarily.
As a preference, the first and second liquid crystal compositions are,
the organic solvent is N-methyl pyrrolidone;
the ultrasonic treatment comprises the following steps: carrying out ultrasonic treatment at the frequency of 42-45 kHz for 50-65 min.
The N-methyl pyrrolidone can dissolve residual glue on the pole piece, copper foil/aluminum foil on the pole piece and the diaphragm, can effectively and thoroughly separate the pole piece and the diaphragm, the copper foil and the aluminum foil in the ultrasonic treatment of the frequency, and can effectively remove an SEI film on the surface of the negative pole piece.
The invention has the beneficial effects that:
1) the whole method is simple and efficient;
2) the nondestructive separation and disassembly of the negative plate can be realized;
3) the residual impurity content on the surface of the negative plate is low, and the negative plate can be directly used for preparing a new battery.
Detailed Description
The present invention will be described in further detail with reference to specific examples. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Unless otherwise specified, the raw materials used in the examples of the present invention are all commercially available or available to those skilled in the art; unless otherwise specified, the methods used in the examples of the present invention are all those known to those skilled in the art.
Example 1
A nondestructive disassembly method for a retired power lithium battery negative plate comprises the following steps:
the method comprises the steps of carrying out preliminary disassembly on a decommissioned power lithium battery, wherein the preliminary disassembly process comprises removing a shell, a gasket and a sealing plate of the decommissioned power lithium battery to obtain a pole piece/diaphragm composition, sequentially freezing the pole piece/diaphragm composition for 22h at 0 ℃ and 0.2atm, heating to 100 ℃ at a heating rate of 5 ℃/min, preserving heat for 20min, freezing at-8 ℃ for 20min, heating to 150 ℃ at a heating rate of 5 ℃/min, preserving heat for 20min, finally freezing at-20 ℃ for 30min, keeping the temperature of the pole piece/diaphragm composition below 4 ℃ after treatment, placing the pole piece/diaphragm composition in N-methyl pyrrolidone for 42kHz ultrasonic treatment for 65min, separating a pole piece from a diaphragm, and obtaining a negative pole piece through nondestructive disassembly.
Example 2
A nondestructive disassembly method for a retired power lithium battery negative plate comprises the following steps:
the method comprises the steps of carrying out preliminary disassembly on a decommissioned power lithium battery, wherein the preliminary disassembly process comprises removing a shell, a gasket and a sealing plate of the decommissioned power lithium battery to obtain a pole piece/diaphragm composition, sequentially freezing the pole piece/diaphragm composition for 26h at 4 ℃ and 0.25atm, heating to 90 ℃ at a heating rate of 10 ℃/min, carrying out heat preservation for 30min, freezing at-5 ℃ for 30min, heating to 130 ℃ at a heating rate of 10 ℃/min, carrying out heat preservation for 30min, finally carrying out freezing at-18 ℃ for 35min, keeping the temperature of the pole piece/diaphragm composition below 4 ℃ after treatment, placing in N-methylpyrrolidone, carrying out ultrasonic treatment at a frequency of 45kHz for 50min, separating a pole piece from a diaphragm, and obtaining a negative pole piece through nondestructive disassembly.
Example 3
A nondestructive disassembly method for a retired power lithium battery negative plate comprises the following steps:
the method comprises the steps of carrying out preliminary disassembly on a decommissioned power lithium battery, wherein the preliminary disassembly process comprises removing a shell, a gasket and a sealing plate of the decommissioned power lithium battery to obtain a pole piece/diaphragm composition, sequentially freezing the pole piece/diaphragm composition for 24 hours at 0 ℃ and 0.2atm, heating to 90 ℃ at a heating rate of 10 ℃/min, preserving heat for 30min, freezing at-8 ℃ for 30min, heating to 130 ℃ at a heating rate of 10 ℃/min, preserving heat for 30min, finally freezing at-20 ℃ for 35min, keeping the temperature of the pole piece/diaphragm composition below 4 ℃ after treatment, placing the pole piece/diaphragm composition in N-methyl pyrrolidone for ultrasonic treatment at a frequency of 45kHz for 60min, separating a pole piece from a diaphragm, and obtaining a negative pole piece through nondestructive disassembly.
Example 4
A nondestructive disassembly method for a retired power lithium battery negative plate comprises the following steps:
the method comprises the steps of carrying out preliminary disassembly on a decommissioned power lithium battery, wherein the preliminary disassembly process comprises removing a shell, a gasket and a sealing plate of the decommissioned power lithium battery to obtain a pole piece/diaphragm composition, sequentially freezing the pole piece/diaphragm composition for 24 hours at 0 ℃ and 0.2atm, heating to 100 ℃ at a heating rate of 10 ℃/min, preserving heat for 30min, freezing at-8 ℃ for 30min, heating to 150 ℃ at a heating rate of 10 ℃/min, preserving heat for 30min, finally freezing at-20 ℃ for 35min, keeping the temperature of the pole piece/diaphragm composition below 4 ℃ after treatment, placing the pole piece/diaphragm composition in N-methyl pyrrolidone for ultrasonic treatment at a frequency of 45kHz for 60min, separating a pole piece from a diaphragm, and obtaining a negative pole piece through nondestructive disassembly.
Example 5
A nondestructive disassembly method for a retired power lithium battery negative plate comprises the following steps:
the method comprises the steps of carrying out preliminary disassembly on a decommissioned power lithium battery, wherein the preliminary disassembly process comprises removing a shell, a gasket and a sealing plate of the decommissioned power lithium battery to obtain a pole piece/diaphragm composition, sequentially freezing the pole piece/diaphragm composition for 24 hours at 0 ℃ and 0.2atm, heating to 90 ℃ at a heating rate of 5 ℃/min, preserving heat for 30min, freezing at-8 ℃ for 30min, heating to 130 ℃ at a heating rate of 5 ℃/min, preserving heat for 30min, finally freezing at-20 ℃ for 35min, keeping the temperature of the pole piece/diaphragm composition below 4 ℃ after treatment, placing the pole piece/diaphragm composition in N-methyl pyrrolidone for ultrasonic treatment at a frequency of 45kHz for 60min, separating a pole piece from a diaphragm, and obtaining a negative pole piece through nondestructive disassembly.
Comparative example 1
The specific procedure was the same as in example 3, except that: the organic solvent is absolute ethyl alcohol.
Comparative example 2
The specific procedure was the same as in example 3, except that: the ultrasonic frequency was 35 kHz.
The above examples 1-5 and comparative examples 1-2 were all tested using 20 electrode sheet/separator compositions.
And detecting and counting the negative plates obtained by the separation of the examples 1-5 and the comparative examples 1-2.
According to statistics, the separation rate of the negative plates in the embodiments 1 to 5 is 100%, the separation rate of the negative plate in the scheme of the comparative example 1 is 75%, wherein the copper foil on the negative plate obtained after the separation of the two pole plate/diaphragm compositions still adheres to the surface of the negative plate, and the separation rate of the negative plate in the scheme of the comparative example 2 is 100%.
The obtained negative electrode plate is observed by naked eyes and counted, the damage rate of the negative electrode plate in the examples 1-5 is 0%, the damage rate of the negative electrode plate in the scheme of the comparative example 1 is 5%, and the damage rate of the negative electrode plate in the comparative example 2 is 0%.
Impurity detection is carried out on the surface of the obtained negative plate, organic impurities exist on the surface of the negative plate which is completely separated in the comparative example 1 and the comparative example 2, the impurity content on the surface of the comparative example 2 is obviously redundant in the comparative example 1, organic impurities do not exist in the examples 1-5, and the organic impurities are residual glue and/or SEI film residues.

Claims (8)

1. A nondestructive disassembly method for a retired power lithium battery negative plate is characterized in that,
the method comprises the following steps:
the method comprises the following steps of performing initial disassembly on a retired power lithium battery to obtain a pole piece/diaphragm composition, sequentially performing one-stage freezing, one-stage heating, two-stage freezing, two-stage heating and three-stage freezing treatment on the pole piece/diaphragm composition, placing the pole piece/diaphragm composition in an organic solvent for ultrasonic treatment after treatment, separating a pole piece from a diaphragm, and performing nondestructive disassembly to obtain a negative pole piece.
2. The method for nondestructively disassembling a negative plate of a decommissioned power lithium battery according to claim 1,
the preliminary disassembly process comprises removing the casing, the gasket and the sealing plate of the retired power lithium battery.
3. The method for nondestructively disassembling a negative plate of a decommissioned power lithium battery according to claim 1,
the first-stage freezing comprises the following steps: freezing the mixture at 0-4 ℃ and 0.2-0.25 atm for 22-26 h.
4. The method for nondestructively disassembling a negative plate of a decommissioned power lithium battery according to claim 1,
the first-stage heating comprises the following steps: heating to 90-100 ℃ at a heating rate of 5-10 ℃/min, and preserving the heat for 20-30 min.
5. The method for nondestructively disassembling a negative plate of a decommissioned power lithium battery according to claim 1,
the two-stage freezing comprises the following steps: freezing for 20-30 min at-8 to-5 ℃.
6. The method for nondestructively disassembling a negative plate of a decommissioned power lithium battery according to claim 1,
the two-stage heating comprises the following steps: heating to 130-150 ℃ at a heating rate of 5-10 ℃/min, and preserving the heat for 20-30 min.
7. The method for nondestructively disassembling a negative plate of a decommissioned power lithium battery according to claim 1,
the three-stage freezing is as follows: freezing for 30-35 min at-20 to-18 ℃.
8. The method for nondestructively disassembling a negative plate of a decommissioned power lithium battery according to claim 1,
the organic solvent is N-methyl pyrrolidone;
the ultrasonic treatment comprises the following steps: carrying out ultrasonic treatment at the frequency of 42-45 kHz for 50-65 min.
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CN112687974A (en) * 2021-03-16 2021-04-20 嘉兴模度新能源有限公司 Chemical disassembling method applied to battery adhesive module
CN117337510A (en) * 2023-08-25 2024-01-02 广东邦普循环科技有限公司 A device and method for stripping waste lithium-ion battery aluminum foil and cathode materials based on full-chain integration
CN120984659A (en) * 2025-08-21 2025-11-21 成都晶信明能光伏科技有限公司 Recycling methods for the bottom cell in perovskite tandem solar cells

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