CN111224188A - Green recovery process of waste power lithium battery - Google Patents
Green recovery process of waste power lithium battery Download PDFInfo
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- CN111224188A CN111224188A CN202010031894.6A CN202010031894A CN111224188A CN 111224188 A CN111224188 A CN 111224188A CN 202010031894 A CN202010031894 A CN 202010031894A CN 111224188 A CN111224188 A CN 111224188A
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- waste power
- power lithium
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- battery
- drying
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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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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
Abstract
The invention discloses a green recovery process of waste power lithium batteries, which mainly comprises the following steps: (1): cutting and decomposing the shell of the waste power lithium battery to obtain a battery inner core; (2): drying the battery inner core; (3): unwinding the dried battery inner core, and separately collecting the decomposed positive plate and negative plate; (4) independently drying the positive plate/the negative plate; (5): carrying out impact crushing on the dried positive plate/negative plate; (6): and vibrating and screening the crushed positive electrode/negative electrode product to obtain a corresponding separation product. According to the invention, through the modes of separating the positive electrode material and the negative electrode material, then separately collecting, heating, crushing and vibrating screening, the problems that the existing method does not consider electrolyte, the crushing efficiency of the positive electrode plate and the negative electrode plate is not high, the accuracy rate of separating crushed particles is not high and the like are solved, so that the crushing efficiency is improved, the subsequent screening difficulty is reduced, and the recovery efficiency of the waste power battery is improved.
Description
Technical Field
The invention relates to the technical field of lithium battery recovery, in particular to a green recovery process of waste power lithium batteries.
Background
With the rapid increase of the yield of the electric vehicle, the shipment volume of the power battery serving as one of three large core components of the new energy vehicle will also increase greatly, and meanwhile, the first batch of power lithium batteries have reached the retirement stage. In 2020, the power storage batteries of the first new energy vehicles in China are expected to meet a round of 'retired tide', the number of retired batteries is about 20 ten thousand tons, the large-scale waste power lithium batteries need to be treated urgently at present, the existing recovery process method is still immature, the recovery rate is not high, and the problem of recycling of the waste power lithium batteries becomes a key problem.
If the waste power battery is not properly disposed, organic matters and precious metals contained in the waste power battery can pose potential threats to the environment, and on the other hand, aluminum and lithium iron phosphate in the positive plate and copper and graphite in the negative plate of the waste power battery have extremely high recovery values. The waste batteries are recycled, so that the damage to the ecological environment can be reduced, the resources are saved, and the ecological, green and circular production requirements are met. Therefore, it is very necessary to find a green, environment-friendly and efficient method for recovering waste power lithium batteries.
The current recovery methods mainly include mechanical methods, wet methods and biological methods. The wet recovery needs to consume a large amount of strong acid, strong base, extractant and the like, and also generates a large amount of waste liquid, so that the subsequent treatment is difficult. The biological method for recycling uses biological acid to replace the traditional sulfuric acid and nitric acid, has small influence on the environment, but has the defects of difficult culture of biological bacteria, pertinence in recycling, narrow application range and low efficiency. The mechanical principle adopts a mechanical crushing type, the whole electrode (namely, a battery inner core comprising a positive plate, a negative plate and a diaphragm) is crushed and processed, the difficulty of effective separation of electrode material fragments is high in the crushing mode, the separation accuracy is low, and the recycling degree of the waste power lithium battery is low.
The Chinese invention patent with application number of 2019101458704.6: a lithium battery recovery method and equipment disclose the technology that: the positive electrode and the negative electrode are simultaneously crushed to obtain electrode mixed fragments, and the separation of the positive electrode fragments and the negative electrode fragments is realized by a detection method, so that related materials are recovered. The technology still has some technical defects in the practical use process: the battery roll core is firstly crushed, and then the crushed mixed fragments are dried, so that the electrode plates are difficult to crush due to the electrolyte on the surfaces of the electrode plates; the method is realized by adopting an X-ray irradiation method, so that the separation process becomes complicated, the technical requirement is high, and the overlapped and mixed anode and cathode materials are difficult to separate reliably.
Disclosure of Invention
The invention aims to solve the technical problems that the existing method does not consider electrolyte, the crushing efficiency of positive and negative pole pieces is not high, the accuracy rate of separating crushed particles of a battery inner core is not high and the like, so that the crushing efficiency of positive and negative pole materials is improved, the subsequent screening difficulty is reduced, and the recovery efficiency of waste power batteries is improved.
In order to solve the technical problems, the invention adopts a technical scheme that: the green recovery process of the waste power lithium battery mainly comprises the following steps:
(1): cutting and decomposing the shell of the waste power lithium battery to obtain a battery inner core, and directly recycling the shell and the lugs;
(2): drying the battery inner core at 100-140 deg.c for 100-120 min;
(3): unwinding the dried battery inner core in the step (2), separately collecting the decomposed positive plate and negative plate, and directly recovering the decomposed diaphragm;
(4) independently drying the positive plate/the negative plate at the drying temperature of 300-360 ℃ for 60-90 min;
(5): carrying out impact crushing on the positive plate/negative plate dried in the step (4);
(6): and (5) vibrating and screening the crushed positive electrode/negative electrode product in the step (5) to obtain a corresponding separated product.
Preferably, in the step (1), the waste lithium battery is punched and discharged before the housing of the waste lithium battery is cut and decomposed.
Preferably, in the step (2), the drying temperature of the drying treatment of the battery core is 120 ℃, and the drying time is 120 min.
Preferably, in the step (4), the drying temperature of the drying treatment of the positive plate/negative plate is 330 ℃ and the time is 60 min.
Preferably, in the step (5), the breakage ratio of the positive electrode sheet/the negative electrode sheet is 90% or more.
Preferably, after the step (6), the obtained separation product is sorted, and the operations of the step (4) to the step (6) are repeated for the positive electrode plate/the negative electrode plate which is not completely crushed or not completely separated.
Preferably, in the step (2), the electrolyte volatilized in the process of drying the battery core is collected.
Compared with the prior art, the invention has the following beneficial effects:
1. the positive electrode material and the negative electrode material are separated and then respectively crushed, so that the diaphragm can be directly recycled; meanwhile, the broken copper foil and the broken aluminum foil are prevented from being mixed together, the difficulty of subsequent sorting work is greatly reduced, the sorting workload is reduced, and the purities of the copper foil and the aluminum foil are improved;
2. according to the invention, the low-temperature heat treatment is respectively carried out on the positive electrode material and the negative electrode material, so that the bonding effect of the surface binders of the positive electrode sheet and the negative electrode sheet is reduced, substances such as lithium iron phosphate powder on the surface layer of the electrode sheet are easier to separate when being crushed, the crushing efficiency is improved, the bonding phenomenon between crushed products is effectively avoided, and the subsequent vibration screening work is facilitated;
3. according to the invention, the battery inner core is heated, and the heated and volatilized electrolyte is collected, so that the electrolyte is effectively prevented from polluting the environment and damaging the human health, and the cleanness of the environment of the recovery operation site of the waste power lithium battery is ensured.
Drawings
FIG. 1 is a schematic view of the green recycling process of waste power lithium batteries according to the present invention;
FIG. 2 is a diagram showing the anode sheet material of the waste power lithium battery obtained after the battery core is uncoiled and dried;
FIG. 3 is a particle mixture obtained after impact crushing of a positive electrode sheet material of a waste power lithium battery;
fig. 4 shows the waste power lithium battery positive electrode material obtained after the positive electrode particle mixture is subjected to vibration screening.
Detailed Description
The following detailed description of the preferred embodiments of the present invention, taken in conjunction with the accompanying drawings, will make the advantages and features of the invention easier to understand by those skilled in the art, and thus will clearly and clearly define the scope of the invention.
Referring to fig. 1, a green recycling process for waste lithium batteries mainly includes the following steps:
(1): cutting and decomposing the shell of the waste power lithium battery to obtain a battery inner core, and directly recycling the shell and the lugs.
In this embodiment, the housing of the waste power lithium battery is an aluminum housing, the battery core is disposed in the aluminum housing, the battery core includes a positive electrode material, a negative electrode material, and a diaphragm located between the positive electrode material and the negative electrode material, and a tab is disposed at the top of the battery core and used for series/parallel connection between a plurality of lithium battery cell assemblies. The cathode material comprises an aluminum foil and a lithium iron phosphate coating bonded on the surface of the aluminum foil, the anode material comprises a copper foil and a carbon powder coating bonded on the surface of the copper foil, and the binder is polyvinylidene fluoride (PVDF).
Cutting the aluminum shell by cutting equipment (such as a saw blade type cutting machine), taking the battery inner core out of the shell, and cutting and separating the lug from the battery inner core to obtain the battery inner core convenient to unwind; meanwhile, the cut and separated shell and the pole lug can be directly recycled.
Preferably, before cutting and decomposing the shell of the waste power lithium battery, the waste power lithium battery is punched to discharge so that the residual current can be completely released, and personal injury caused by the subsequent cutting and uncoiling processes is avoided. It is obvious that other methods known to the skilled person can be used to achieve the discharge process.
(2): and drying the battery inner core at 100-140 ℃ for 100-120 min.
In this embodiment, the adoption has gas emission and collects the airtight high temperature in structure and space and toasts the case as the drying equipment of battery inner core, can realize the function of rapid heating, temperature regulation and control and tail gas treatment. The battery inner core is being heated the in-process, and the electrolyte on its surface is heated and volatilizees to absorb the processing through the tail gas processing apparatus of constituteing such as deodorization spray column, high flow defroster, active carbon deodorization equipment, exhaust fan, effectively avoided electrolyte polluted environment and harm the health of the person, guarantee the cleanness of useless power lithium cell recovery operation site environment. The high-temperature baking oven and the tail gas treatment device are both existing equipment and are not described in detail herein.
Preferably, the drying temperature of the battery core drying treatment is 120 ℃, and the drying time is 120 min. After the drying operation is finished by adopting the parameters, the surface of the battery inner core is not visually provided with electrolyte residues, so that the subsequent uncoiling operation is facilitated.
(3): and (3) unwinding the dried battery inner core in the step (2), separately collecting the decomposed positive plate and the decomposed negative plate, and directly recovering the decomposed diaphragm.
In this embodiment, the manual unwinding is adopted in the unwinding process of the battery core, so that the positive electrode material, the negative electrode material and the diaphragm positioned between the positive electrode material and the negative electrode material can be perfectly separated, the separated diaphragm can be directly recycled, and the separated positive electrode sheet and the separated negative electrode sheet are separately collected so as to facilitate the subsequent secondary drying operation.
(4) And independently drying the positive plate/the negative plate at the drying temperature of 300-360 ℃ for 60-90 min.
And (3) adopting a high-temperature drying box which is the same as that in the step (2) as drying equipment, and putting the collected positive plate/negative plate into the high-temperature drying box for secondary drying. Preferably, the drying temperature is set to be 330 ℃ and the drying time is set to be 60 min. After the drying operation is completed by adopting the parameters, a large number of cracks appear on the surfaces of the lithium iron phosphate coating on the positive plate and the carbon powder coating on the negative plate, and the lithium iron phosphate coating and the carbon powder coating are in a state of being about to peel off. After the positive plate is dried, the state of the lithium iron phosphate coating is shown in fig. 2.
By respectively carrying out low-temperature heat treatment on the positive electrode material and the negative electrode material, the bonding effect of the surface binders of the positive electrode plate and the negative electrode plate is reduced, so that substances such as lithium iron phosphate powder on the surface layer of the electrode plate are easier to separate when the electrode plate is crushed, the crushing efficiency is improved, the bonding phenomenon between crushed products is effectively avoided, and the subsequent vibration screening work is facilitated.
(5): and (4) carrying out impact crushing on the positive plate/negative plate dried in the step (4).
In this embodiment, a crushing device (e.g., a plastic pendulum impact crusher) is used to crush the dried positive plate/negative plate, so that the crushing ratio of the aluminum foil/copper foil reaches above 90%, at this time, the lithium iron phosphate coating in the positive material becomes powder and is basically and completely separated from the surface of the aluminum foil, and the carbon powder coating in the negative material becomes powder and is basically and completely separated from the surface of the copper foil. The particle mixture obtained after the dried positive plate is crushed by impact is shown in fig. 3.
The positive electrode material and the negative electrode material are separated and then respectively crushed, so that the diaphragm can be directly recycled; meanwhile, the broken copper foil and the broken aluminum foil are prevented from being mixed together, the difficulty of subsequent sorting work is greatly reduced, and the purities of the copper foil and the aluminum foil are improved while the sorting workload is reduced.
(6): and (5) vibrating and screening the crushed positive electrode/negative electrode product in the step (5) to obtain a corresponding separated product.
And (3) vibrating and screening the crushed particle mixture of the positive electrode material by using a vibrating and screening device to obtain aluminum foil fragments and lithium iron phosphate powder, as shown in fig. 4. Similarly, the particle mixture of the negative electrode material was subjected to vibratory screening to obtain copper foil pieces and carbon powder. And respectively recovering and treating the separated products to realize green recovery of the waste power lithium battery.
Preferably, after the vibration screening is completed, the completely crushed positive plate/negative plate is directly collected through a sieve pore, the incompletely crushed or incompletely separated positive plate/negative plate can be recycled through the vibration screen, so that the obtained separation product is sorted, and the operations from the step (4) to the step (6) are repeated to ensure the crushing rate of the positive plate/negative plate and the stripping rate of the surface coating.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (7)
1. A green recovery process of waste power lithium batteries is characterized by comprising the following steps: the process mainly comprises the following steps:
(1): cutting and decomposing the shell of the waste power lithium battery to obtain a battery inner core, and directly recycling the shell and the lugs;
(2): drying the battery inner core at 100-140 deg.c for 100-120 min;
(3): unwinding the dried battery inner core in the step (2), separately collecting the decomposed positive plate and negative plate, and directly recovering the decomposed diaphragm;
(4) independently drying the positive plate/the negative plate at the drying temperature of 300-360 ℃ for 60-90 min;
(5): carrying out impact crushing on the positive plate/negative plate dried in the step (4);
(6): and (5) vibrating and screening the crushed positive electrode/negative electrode product in the step (5) to obtain a corresponding separated product.
2. The green recycling process of waste power lithium batteries as claimed in claim 1, wherein: in the step (1), before the shell of the waste power lithium battery is cut and decomposed, the waste power lithium battery is punched and discharged.
3. The green recycling process of waste power lithium batteries as claimed in claim 1, wherein: in the step (2), the drying temperature of the battery core drying treatment is 120 ℃, and the drying time is 120 min.
4. The green recycling process of waste power lithium batteries as claimed in claim 1, wherein: in the step (4), the drying temperature of the drying treatment of the positive plate/the negative plate is 330 ℃, and the drying time is 60 min.
5. The green recycling process of waste power lithium batteries as claimed in claim 1, wherein: in the step (5), the breakage ratio of the positive electrode sheet/the negative electrode sheet is 90% or more.
6. The green recycling process of waste power lithium batteries as claimed in claim 1, wherein: and (4) after the step (6), sorting the obtained separation product, and repeating the operations from the step (4) to the step (6) on the positive plate/negative plate which is not completely crushed or not completely separated.
7. The green recycling process of waste power lithium batteries as claimed in claim 1, wherein: in the step (2), the electrolyte volatilized in the drying process of the battery inner core is collected and processed.
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| CN202010031894.6A CN111224188A (en) | 2020-01-11 | 2020-01-11 | Green recovery process of waste power lithium battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113270659A (en) * | 2021-05-12 | 2021-08-17 | 湖北融通高科先进材料有限公司 | Method for recycling lithium iron phosphate material by two-step method |
| CN113422120A (en) * | 2021-04-29 | 2021-09-21 | 马鞍山海森控电气有限公司 | Non-destructive lithium battery recovery method |
| CN114243147A (en) * | 2021-12-20 | 2022-03-25 | 武汉蔚能电池资产有限公司 | Lithium battery recovery device and lithium battery recovery method |
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| CN114243147A (en) * | 2021-12-20 | 2022-03-25 | 武汉蔚能电池资产有限公司 | Lithium battery recovery device and lithium battery recovery method |
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Application publication date: 20200602 |