CN114024052A - Waste lithium battery harmless recovery treatment method based on heat treatment - Google Patents
Waste lithium battery harmless recovery treatment method based on heat treatment Download PDFInfo
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- CN114024052A CN114024052A CN202111262589.9A CN202111262589A CN114024052A CN 114024052 A CN114024052 A CN 114024052A CN 202111262589 A CN202111262589 A CN 202111262589A CN 114024052 A CN114024052 A CN 114024052A
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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
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- 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
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- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
本发明公开了一种基于热处理的废旧锂电池无害化回收处理方法，包括以下步骤：(1)废旧锂电池经过放电、拆解后得到外壳、隔膜、电解液、正极材料及负极材料；(2)将得到的外壳和隔膜进行除杂处理，除杂后的外壳与隔膜进行回收再利用；(3)将得到的电解液进行热处理，实现残渣和尾气的无害化排放；将得到的正极材料和负极材料进行混合并破碎，破碎后的样品进行热处理，实现尾气的无害化排放，残渣中正负极粉、铜、铝的回收。本发明在电池有效拆解的基础上，实现可回收组分外壳与隔膜的最大回收力度，有毒有害的电解液的无害化处理与排放，正负极材料的回收，工艺方法操作简单，工艺流程短，易于工业化推广。
The invention discloses a harmless recovery and treatment method for waste lithium batteries based on heat treatment, comprising the following steps: (1) after the waste lithium batteries are discharged and disassembled, a casing, a diaphragm, an electrolyte, a positive electrode material and a negative electrode material are obtained; ( 2) carry out impurity removal treatment with the obtained shell and diaphragm, and recycle and reuse the shell and diaphragm after the impurity removal; (3) heat treatment of the obtained electrolyte to realize the harmless discharge of residue and tail gas; The material and the negative electrode material are mixed and crushed, and the crushed sample is subjected to heat treatment to realize the harmless discharge of exhaust gas and the recovery of positive and negative electrode powder, copper and aluminum in the residue. On the basis of the effective disassembly of the battery, the invention realizes the maximum recovery strength of the recyclable component shell and the diaphragm, the harmless treatment and discharge of the toxic and harmful electrolyte, the recovery of the positive and negative electrode materials, the process method is simple to operate, and the process The process is short, and it is easy to promote industrialization.
Description
Technical Field
The invention relates to the technical field of waste lithium battery recycling, in particular to a waste lithium battery harmless recycling method based on heat treatment.
Background
The revolution in vehicles and the rapid development of energy storage grids has fueled the growth in consumption and demand for lithium batteries, the potential for which is being increasingly driven in the area of power supplies and energy storage devices for electric and hybrid vehicles. Therefore, the number of lithium batteries shows a tendency to explosive growth on a global scale. Correspondingly, the number of lithium batteries in the end of life cycle of the product is also increasing. These large quantities of waste lithium batteries, which are not recycled or disposed of, can have significant negative effects on human health and the environment due to the potential toxic substances and environmental pollutants contained therein. Therefore, effective treatment of spent lithium batteries is a critical environmental issue.
The application of the thermal conversion technology can realize the harmless treatment of the battery difficult-to-treat components and the recycling of effective components, and CN201811416385.4 reports a recycling process of a waste battery anode material, wherein electrode powder is recycled by a pyrolysis method, but other substances in the battery are not recycled. CN202110461107.6 reports a method for separating electrode active substances in waste lithium ion batteries, which comprises the specific steps of firstly removing plastic parts and battery diaphragms to obtain crushed materials, and sending the crushed materials into a multi-hearth furnace for pyrolysis treatment, wherein the multi-hearth furnace comprises 8 layers of structures, each layer of hearth corresponds to different pyrolysis temperatures, the treatment method has complicated temperature program rise, more temperature control variables and complicated operation process, is difficult to realize industrial application, and omits the harmless treatment of electrolyte with great environmental hazard. Aiming at the defect that lithium batteries represented by aluminum shell power lithium batteries, soft package power lithium batteries and 3c lithium batteries lack a comprehensive harmless treatment method of a system.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a waste lithium battery harmless recovery processing method based on heat treatment, which realizes the maximum recovery strength of a recyclable component shell and a diaphragm, the harmless treatment and discharge of toxic and harmful electrolyte and the recovery of positive and negative electrode materials on the basis of the effective disassembly of a battery.
In order to achieve the purpose, the invention adopts the technical scheme that:
a waste lithium battery harmless recovery treatment method based on heat treatment comprises the following steps:
discharging and disassembling the waste lithium battery to obtain a shell, a diaphragm, electrolyte, a positive material and a negative material;
removing impurities from the obtained shell and the obtained diaphragm, and recycling the shell and the diaphragm after impurity removal;
carrying out heat treatment on the obtained electrolyte to realize harmless emission of residues and tail gas;
and mixing and crushing the obtained positive electrode material and negative electrode material, and carrying out heat treatment on the crushed sample to realize harmless emission of tail gas and recovery of positive and negative electrode powder, copper and aluminum in residues.
According to the invention, the plastic shell and the diaphragm are subjected to impurity removal and classified recovery, the electrolyte is subjected to thermal conversion treatment and then discharged harmlessly, and the anode and cathode materials are subjected to thermal conversion treatment and then recovered with anode and cathode powder and copper and aluminum substances, so that harmless and high-quality recycling in the battery recovery process is realized.
Preferably, the waste lithium battery comprises a lithium iron phosphate battery and a ternary lithium ion battery.
Preferably, the shell is made of plastic, and the diaphragm is made of a single-layer polyethylene, polypropylene microporous film or polypropylene/polyethylene/polypropylene three-layer microporous composite film.
Preferably, the heat treatment temperature of the electrolyte is 300-600 ℃, the time is 2-4 hours, the atmosphere is inert gas, the generated gas is discharged after dust removal, spraying, activated carbon adsorption and fluorine and phosphorus absorption treatment, and the generated residue is used as a building material.
Preferably, the heat treatment temperature of the sample is 400-600 ℃, the pyrolysis time is 2-4 hours, the atmosphere is inert gas, in order to improve the separation efficiency of the current collector and the active substance, water with the mass of 5-8% of the raw material is added in the thermal conversion process, the generated gas is discharged after dust removal, spraying and activated carbon adsorption, and the generated residues are ground and screened to obtain anode and cathode powder, copper and aluminum.
Preferably, the inert gas is nitrogen or argon.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention realizes the recycling of effective components of the battery and the harmless treatment and discharge of pollution components to the maximum extent, wherein the plastic shell and the diaphragm are subjected to impurity removal and classified recovery; the electrolyte is subjected to thermal conversion treatment and then is discharged harmlessly; the positive and negative electrode materials are subjected to thermal conversion treatment to recover positive and negative electrode powder and copper and aluminum substances, the recovery rate of the positive and negative electrode powder is more than 97 wt%, and the recovery rate of the copper and aluminum is more than 96 wt%.
2) The treatment method is simple, low in energy consumption and pollution-free, residues obtained after the electrolyte is subjected to heat treatment can be safely used for building materials, and the generated tail gas can reach the standard and be discharged after being treated; the anode powder obtained by heat treatment of the anode and cathode materials is pure and easy to regenerate, the obtained residues are easy to peel off, the separation of the anode and cathode powder and the current collector can be realized through conventional simple screening, and the obtained anode and cathode powder does not contain other substances except carbon, so that the recycling of the anode and cathode active substances is facilitated.
3) According to the invention, a certain amount of water is added in the heat treatment of the anode and cathode materials, so that pyrolysis products such as organic binders and active substances can easily fall off from the pole piece, and the separation of the pyrolysis products and the current collector is realized; meanwhile, the added water does not have any adverse effect on the copper and aluminum current collectors and the positive and negative electrode active substances, and the recycling value of the copper and aluminum current collectors and the positive and negative electrode active substances is not influenced.
Drawings
FIG. 1 is a process flow diagram of the process of the present invention.
Detailed Description
In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention is further described in detail below with reference to the accompanying drawings and the detailed description.
Example 1
(1) The waste lithium iron phosphate battery is subjected to overdischarge and disassembly steps to obtain plastic shells, polyethylene diaphragms, electrolyte, positive electrode materials and negative electrode material components;
(2) removing impurities from the plastic shell and the polyethylene diaphragm, and classifying and recycling the plastic shell and the polyethylene diaphragm;
(3) carrying out heat treatment on the electrolyte obtained by separation in a fixed bed, wherein the heat treatment atmosphere is nitrogen, the temperature is 300 ℃, the heat preservation time is 4 hours, the tail gas generated after the treatment is discharged after dust removal, spraying, activated carbon adsorption and fluorine and phosphorus absorption treatment, and the generated residue can be used as a building material;
(4) mixing and crushing the separated positive and negative electrode materials, putting the mixture into a fixed bed for heat treatment, wherein the heat treatment atmosphere is nitrogen, the temperature is 400 ℃, the added water amount is 5 percent of the mass of the raw materials, the heat preservation time is 4 hours, the generated gas is discharged after dedusting, spraying and activated carbon adsorption, and the generated residues are ground and screened to obtain positive and negative electrode powder, copper and aluminum, wherein the recovery rate of the positive and negative electrode powder is 97 weight percent, and the recovery rate of the copper and the aluminum is 96 weight percent.
Example 2
(1) The waste ternary lithium ion battery is subjected to overdischarge and disassembly steps to obtain plastic shells, polypropylene diaphragms, electrolyte, positive electrode materials and negative electrode material components;
(2) removing impurities from the plastic shell and the polypropylene diaphragm, and classifying and recycling the plastic shell and the polypropylene diaphragm;
(3) carrying out heat treatment on the electrolyte obtained by separation in a fixed bed, wherein the heat treatment atmosphere is argon, the temperature is 500 ℃, the heat preservation time is 2 hours, the tail gas generated after the treatment is discharged after dust removal, spraying, activated carbon adsorption and fluorine and phosphorus absorption treatment, and the generated residue can be used as a building material;
(4) mixing and crushing the separated positive and negative electrode materials, putting the mixture into a fixed bed for heat treatment, wherein the heat treatment atmosphere is argon, the temperature is 600 ℃, the added water amount is 8 percent of the mass of the raw materials, the heat preservation time is 2 hours, the generated gas is discharged after dedusting, spraying and activated carbon adsorption, and the generated residues are ground and screened to obtain positive and negative electrode powder, copper and aluminum, wherein the recovery rate of the positive and negative electrode powder is 98 weight percent, and the recovery rate of the copper and the aluminum is 98 weight percent.
Example 3
(1) The waste ternary lithium ion battery is subjected to overdischarge and disassembly steps to obtain plastic shells, polypropylene/polyethylene/polypropylene composite diaphragms, electrolyte, positive electrode materials and negative electrode material components;
(2) removing impurities from the plastic shell and the polypropylene/polyethylene/polypropylene composite diaphragm, and classifying and recycling the plastic shell and the polypropylene/polyethylene/polypropylene composite diaphragm;
(3) carrying out heat treatment on the electrolyte obtained by separation in a fixed bed, wherein the heat treatment atmosphere is argon, the temperature is 400 ℃, the heat preservation time is 3 hours, the tail gas generated after the treatment is discharged after dust removal, spraying, activated carbon adsorption and fluorine and phosphorus absorption treatment, and the generated residue can be used as a building material;
(4) mixing and crushing the separated positive and negative electrode materials, putting the mixture into a fixed bed for heat treatment, wherein the heat treatment atmosphere is argon, the temperature is 500 ℃, the added water amount is 6 percent of the mass of the raw materials, the heat preservation time is 3 hours, the generated gas is discharged after dedusting, spraying and activated carbon adsorption, and the generated residues are ground and screened to obtain positive and negative electrode powder, copper and aluminum, wherein the recovery rate of the positive and negative electrode powder is 99 weight percent, and the recovery rate of the copper and the aluminum is 99 weight percent.
Example 4
(1) The waste lithium iron phosphate battery is subjected to overdischarge and disassembly steps to obtain plastic shells, polypropylene/polyethylene/polypropylene composite diaphragms, electrolyte, positive electrode materials and negative electrode material components;
(2) removing impurities from the plastic shell and the polypropylene/polyethylene/polypropylene composite diaphragm, and classifying and recycling the plastic shell and the polypropylene/polyethylene/polypropylene composite diaphragm;
(3) and (3) carrying out heat treatment on the electrolyte obtained by separation in a fixed bed, wherein the heat treatment atmosphere is nitrogen, the temperature is 600 ℃, the heat preservation time is 2 hours, the tail gas generated after the treatment is subjected to dust removal, spraying, activated carbon adsorption and fluorine and phosphorus absorption treatment and then is discharged, and the generated residues can be used as building materials.
(4) Mixing and crushing the separated positive and negative electrode materials, putting the mixture into a fixed bed for heat treatment, wherein the heat treatment atmosphere is argon, the temperature is 500 ℃, the added water amount is 7 percent of the mass of the raw materials, the heat preservation time is 4 hours, the generated gas is discharged after dedusting, spraying and activated carbon adsorption, and the generated residues are ground and screened to obtain positive and negative electrode powder, copper and aluminum, wherein the recovery rate of the positive and negative electrode powder is 98 weight percent, and the recovery rate of the copper and the aluminum is 97 weight percent.
The above embodiments are only for illustrating the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention accordingly, and not to limit the protection scope of the present invention accordingly. All equivalent changes or modifications made in accordance with the spirit of the present disclosure are intended to be covered by the scope of the present disclosure.
Claims (6)
1. A waste lithium battery harmless recovery processing method based on heat treatment is characterized by comprising the following steps: the method comprises the following steps:
discharging and disassembling the waste lithium battery to obtain a shell, a diaphragm, electrolyte, a positive material and a negative material;
removing impurities from the obtained shell and the obtained diaphragm, and recycling the shell and the diaphragm after impurity removal;
carrying out heat treatment on the obtained electrolyte to realize harmless emission of residues and tail gas;
and mixing and crushing the obtained positive electrode material and negative electrode material, and carrying out heat treatment on the crushed sample to realize harmless emission of tail gas and recovery of positive and negative electrode powder, copper and aluminum in residues.
2. The method for the harmless recovery and treatment of the waste lithium batteries based on the heat treatment as claimed in claim 1, wherein the method comprises the following steps: the waste lithium battery comprises a lithium iron phosphate battery and a ternary lithium ion battery.
3. The heat treatment-based method for repairing and regenerating the positive electrode material of the waste lithium battery based on heat treatment as claimed in claim 1, wherein the method comprises the following steps: the shell is made of plastic, and the diaphragm is made of a single-layer polyethylene, polypropylene microporous film or polypropylene/polyethylene/polypropylene three-layer microporous composite film.
4. The heat treatment-based method for repairing and regenerating the positive electrode material of the waste lithium battery based on heat treatment as claimed in claim 1, wherein the method comprises the following steps: the heat treatment temperature of the electrolyte is 300-600 ℃, the time is 2-4 hours, the atmosphere is inert gas, the generated gas is discharged after dust removal, spraying, activated carbon adsorption and fluorine and phosphorus absorption treatment, and the generated residues are used as building materials.
5. The heat treatment-based method for repairing and regenerating the positive electrode material of the waste lithium battery based on heat treatment as claimed in claim 1, wherein the method comprises the following steps: the heat treatment temperature of the sample is 400-.
6. The heat treatment based waste lithium battery positive electrode material heat treatment restoration and regeneration method as claimed in claim 4 or 5, is characterized in that: the inert gas is nitrogen or argon.
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Cited By (3)
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| CN115498303A (en) * | 2022-10-31 | 2022-12-20 | 杰瑞环保科技有限公司 | Lithium battery recycling method |
| CN115663324A (en) * | 2022-08-05 | 2023-01-31 | 西安交通大学 | Restoration and regeneration process for retired battery diaphragm |
| WO2024092452A1 (en) * | 2022-10-31 | 2024-05-10 | 杰瑞环保科技有限公司 | Lithium battery recycling method |
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