CN116914308B - Recovery method of graphite cathode of lithium ion battery - Google Patents
Recovery method of graphite cathode of lithium ion battery Download PDFInfo
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- CN116914308B CN116914308B CN202311181878.5A CN202311181878A CN116914308B CN 116914308 B CN116914308 B CN 116914308B CN 202311181878 A CN202311181878 A CN 202311181878A CN 116914308 B CN116914308 B CN 116914308B
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- 238000000034 method Methods 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 27
- 239000010439 graphite Substances 0.000 title claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 27
- 238000011084 recovery Methods 0.000 title claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 41
- 238000010438 heat treatment Methods 0.000 claims abstract description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000011889 copper foil Substances 0.000 claims abstract description 25
- 239000007773 negative electrode material Substances 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 238000004064 recycling Methods 0.000 claims abstract description 11
- 238000002791 soaking Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000498 ball milling Methods 0.000 claims description 20
- 239000006183 anode active material Substances 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000000197 pyrolysis Methods 0.000 claims description 8
- -1 polypropylene Polymers 0.000 claims description 7
- 239000011324 bead Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 30
- 239000012528 membrane Substances 0.000 description 15
- 238000003763 carbonization Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- 239000005041 Mylar™ Substances 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of material recovery. In particular to a method for recycling graphite cathodes of lithium ion batteries, which comprises the following steps: s1: disassembling the lithium ion battery, and removing the shell to obtain a bare cell; s2: stripping the positive electrode plate, and reserving the negative electrode plate and the diaphragm to keep the negative electrode plate and the diaphragm in an adhesion state so as to obtain a composite negative electrode plate adhered with the diaphragm; s3: tiling the composite negative electrode plate, and keeping the diaphragm in the composite negative electrode plate in an upward state; s4: heating the tiled composite negative electrode plate to completely melt the diaphragm, and then cooling to resolidify the melted diaphragm to obtain a secondary composite film; s5: soaking the obtained secondary composite film in water, removing the film to separate the melted and resolidified diaphragm together with the negative electrode active material layer and the copper foil, and removing the copper foil to obtain the negative electrode active material layer adhered with the diaphragm; and then heating and pyrolyzing the lithium ion battery to carbonize the diaphragm, thus completing the recovery of the graphite cathode of the lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of material recovery. More particularly, to a method for recycling graphite cathodes of lithium ion batteries.
Background
The recovery process of the lithium ion battery can be generally divided into pretreatment, impurity removal and recycling. In the pretreatment stage, the lithium ion battery still has residual electric quantity, and in order to avoid the safety problems such as short circuit or spontaneous combustion in the disassembly process, the lithium ion battery is fully discharged by adopting an internal short circuit or salt solution soaking mode. After the battery is completely discharged, the waste graphite black powder is obtained through the treatment modes of manual disassembly, mechanical crushing, screening and the like. In the whole process, some metal impurities (lithium, aluminum, cobalt, nickel, copper and the like), organic electrolyte, binder and the like are inevitably mixed in the graphite again, so that the subsequent material recovery efficiency is affected.
The copper is mainly introduced, and the reason is that the negative electrode plate takes copper foil with the thickness of 6-12 mu m as a current collector, graphite is adhered to the surface of the copper foil through an adhesive, and when the copper foil is separated, part of the copper foil and the graphite are difficult to effectively separate, so that the copper foil is introduced into the final graphite black powder, and the copper impurity exceeds standard. In order to avoid the introduction of copper as far as possible, the aim of removing trace metal impurities in graphite is fulfilled by recovering the copper foil of the negative current collector through a heat treatment or acid leaching process in the prior art; the adhesion force of the copper foil and the graphite interface is weakened by adopting an electrolysis process, so that the desorption purpose is achieved; the former is a big problem in environmental protection due to the need of frequent use of a large amount of acid solution; in the industrial engineering, the disassembled pole piece is difficult to ensure the integrity, the assembly of the pole piece into the material for electrolysis is time-consuming and labor-consuming, and the electrolysis energy consumption is also a great difficulty.
Therefore, developing a simple and rapid recovery mode capable of separating graphite from copper foil is one of the bottleneck problems of limiting recovery and regeneration of materials in the field of lithium ion batteries.
Disclosure of Invention
The invention aims to solve the technical problems that: the invention provides a method for recycling a graphite negative electrode of a lithium ion battery, which solves the problem that a copper foil is difficult to separate from a negative electrode active material layer simply and efficiently in the recycling process of the graphite negative electrode of the existing lithium ion battery.
The invention aims to provide a method for recycling a graphite negative electrode of a lithium ion battery.
The above object of the present invention is achieved by the following technical scheme: the method for recycling the graphite cathode of the lithium ion battery comprises the following steps: s1: disassembling the lithium ion battery, and removing the shell to obtain a bare cell; the bare cell comprises a positive pole piece, a negative pole piece and a diaphragm arranged between the positive pole piece and the negative pole piece; s2: stripping the positive electrode plate, and reserving the negative electrode plate and the diaphragm to keep the positive electrode plate and the diaphragm in an adhesion state so as to obtain a composite negative electrode plate adhered with the diaphragm; s3: tiling the composite negative electrode plate, keeping the composite negative electrode plate in a state that the negative electrode plate is positioned at the bottom and the diaphragm is positioned at the top of the negative electrode plate; s4: heating the tiled composite negative electrode plate to completely melt the diaphragm, and then cooling to resolidify the melted diaphragm to obtain a secondary composite film; s5: soaking the obtained secondary composite film in water, removing the film to separate the melted and resolidified diaphragm together with the negative electrode active material layer and the copper foil, and removing the copper foil to obtain the negative electrode active material layer adhered with the diaphragm; and then heating and pyrolyzing the lithium ion battery to carbonize the diaphragm, thus completing the recovery of the graphite cathode of the lithium ion battery.
According to the technical scheme, only the positive electrode plate is peeled off and removed in the process of disassembling the battery core, so that the diaphragm and the negative electrode are still in an adhesion state, the diaphragm is melted by heating, so that firm adhesion is formed on the surface of the negative electrode active material layer by using the melted diaphragm, after cooling, the melted diaphragm is firmly adhered on the surface of the negative electrode active material layer, and is hardened to form a continuous surface film layer, so that the adhesive force of an adhesive in the negative electrode active material layer is weakened by soaking in water, the adhesion between the negative electrode active material layer and the copper foil is weakened, and the film is removed by using the hardened continuous film layer, so that the negative electrode active material layer is continuously and easily separated from the surface of the copper foil; finally, the hardened separator on the surface of the anode active material layer is converted into a carbonaceous component by carbonization and pyrolysis. The recovery process skillfully utilizes the plastic diaphragm existing in the battery cell, utilizes the thermoplastic property of the battery cell, assists the negative electrode active material to be complete, continuously and rapidly fall off from the surface of the copper foil, and finally enables the components to be directly acted and recovered together with graphite through pyrolysis carbonization.
Further, in the step S4, the heating includes: and (3) adopting flat plate heating, pressing a heating plate on the surface of the diaphragm, and maintaining the pressure of 0.03-0.05MPa in the heating process.
According to the scheme, the flat plate with certain pressure is matched with the heating process, so that the diaphragm with the molten surface layer can form a continuous adhesive layer on the surface of the anode active material layer, and meanwhile, the adhesive force between the adhesive layer and the anode active material layer can be improved, so that the adhesive layer and the anode active material layer are firmly combined, and the diaphragm can be conveniently and rapidly opened continuously in the subsequent film opening process.
Further, in the step S4, the cooling includes: the plate heating is stopped, allowed to cool naturally, and the pressure is maintained during the cooling.
In the cooling process, the pressure is continuously maintained, and the phenomenon that the local diaphragm is warped due to stress release, so that the local diaphragm is failed to uncover due to poor adhesion between the local diaphragm and the anode active material layer is avoided.
Further, in the step S5, the thermal pyrolysis includes: pyrolysis is carried out at 800-1200 ℃ under the protection of inert gas.
Further, in the step S5, the separator-adhered anode active material layer is ball-milled and mixed before the thermal pyrolysis is performed.
Further, the ball-milling mixing includes: the mass ratio of the ball materials is 20:1-30:1 adding zirconia ball-milling beads, and ball-milling and mixing for 2-4 hours under the condition that the ball-milling rotating speed is 400-600r/min to obtain the ball grinding material.
Further, the separator includes a base film, which is any one of a polypropylene base film or a polyethylene base film.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1
Selecting a square aluminum shell battery as a disassembled and recycled object, firstly cutting a cover plate of the battery by adopting cutting equipment, and removing a battery shell to obtain a bare cell comprising a positive pole piece, a negative pole piece and a diaphragm arranged between the positive pole piece and the negative pole piece; the separator includes a base film that is a polypropylene base film.
And (3) peeling off the mylar film wrapped on the surface of the bare cell, tearing off the ending adhesive tape, opening the cell, peeling off and removing the positive pole piece, and reserving the negative pole piece and the diaphragm to keep the negative pole piece and the diaphragm in an adhesion state so as to obtain the composite negative pole piece adhered with the diaphragm.
And tiling the composite negative electrode plate, keeping the composite negative electrode plate in a state that the negative electrode plate is positioned at the bottom and the diaphragm is positioned at the top of the negative electrode plate.
Heating the tiled composite negative electrode plate to enable the diaphragm to be completely melted, specifically, adopting flat plate heating to press a heating plate on the surface of the diaphragm, and keeping the pressure of 0.03MPa in the heating process; and then stopping heating the flat plate, and cooling to resolidify the melted diaphragm, and maintaining the pressure during cooling to obtain the secondary composite film.
Soaking the obtained secondary composite membrane in water, continuously soaking for 6 hours at the temperature of 45 ℃, taking out the secondary composite membrane, uncovering the membrane to separate the melted and resolidified membrane together with the negative electrode active material layer from the copper foil, and removing the copper foil to obtain the negative electrode active material layer adhered with the membrane; transferring the anode active material layer adhered with the diaphragm into a ball milling tank, and mixing the anode active material layer and the ball material layer according to the mass ratio of 20:1 adding zirconia ball-milling beads, and ball-milling and mixing for 2 hours under the condition that the ball-milling rotating speed is 400r/min to obtain a ball grinding material; and transferring the ball-milled material into a carbonization furnace, pyrolyzing the ball-milled material at 800 ℃ under the protection of nitrogen gas for 4 hours, cooling the ball-milled material to room temperature along with the furnace, and discharging the ball-milled material to finish the recovery of the graphite cathode of the lithium ion battery.
Example 2
Selecting a square aluminum shell battery as a disassembled and recycled object, firstly cutting a cover plate of the battery by adopting cutting equipment, and removing a battery shell to obtain a bare cell comprising a positive pole piece, a negative pole piece and a diaphragm arranged between the positive pole piece and the negative pole piece; the separator includes a base film, which is a polyethylene-based film.
And (3) peeling off the mylar film wrapped on the surface of the bare cell, tearing off the ending adhesive tape, opening the cell, peeling off and removing the positive pole piece, and reserving the negative pole piece and the diaphragm to keep the negative pole piece and the diaphragm in an adhesion state so as to obtain the composite negative pole piece adhered with the diaphragm.
And tiling the composite negative electrode plate, keeping the composite negative electrode plate in a state that the negative electrode plate is positioned at the bottom and the diaphragm is positioned at the top of the negative electrode plate.
Heating the tiled composite negative electrode plate to enable the diaphragm to be completely melted, specifically, adopting flat plate heating to press a heating plate on the surface of the diaphragm, and keeping the pressure of 0.04MPa in the heating process; and then stopping heating the flat plate, and cooling to resolidify the melted diaphragm, and maintaining the pressure during cooling to obtain the secondary composite film.
Soaking the obtained secondary composite membrane in water, continuously soaking for 7 hours at 50 ℃, taking out the secondary composite membrane, uncovering the membrane to separate the melted and resolidified membrane together with the negative electrode active material layer from the copper foil, and removing the copper foil to obtain the negative electrode active material layer adhered with the membrane; transferring the anode active material layer adhered with the diaphragm into a ball milling tank, and mixing the anode active material layer and the ball material layer according to the mass ratio of 25:1 adding zirconia ball-milling beads, and ball-milling and mixing for 3 hours under the condition that the ball-milling rotating speed is 500r/min to obtain a ball grinding material; and transferring the ball-milled material into a carbonization furnace, pyrolyzing the ball-milled material at the temperature of 1000 ℃ under the protection of nitrogen gas for 5 hours, cooling the ball-milled material to room temperature along with the furnace, and discharging the ball-milled material to finish the recovery of the graphite cathode of the lithium ion battery.
Example 3
Selecting a square aluminum shell battery as a disassembled and recycled object, firstly cutting a cover plate of the battery by adopting cutting equipment, and removing a battery shell to obtain a bare cell comprising a positive pole piece, a negative pole piece and a diaphragm arranged between the positive pole piece and the negative pole piece; the separator includes a base film that is a polypropylene base film.
And (3) peeling off the mylar film wrapped on the surface of the bare cell, tearing off the ending adhesive tape, opening the cell, peeling off and removing the positive pole piece, and reserving the negative pole piece and the diaphragm to keep the negative pole piece and the diaphragm in an adhesion state so as to obtain the composite negative pole piece adhered with the diaphragm.
And tiling the composite negative electrode plate, keeping the composite negative electrode plate in a state that the negative electrode plate is positioned at the bottom and the diaphragm is positioned at the top of the negative electrode plate.
Heating the tiled composite negative electrode plate to enable the diaphragm to be completely melted, specifically, adopting flat plate heating to press a heating plate on the surface of the diaphragm, and keeping the pressure of 0.05MPa in the heating process; and then stopping heating the flat plate, and cooling to resolidify the melted diaphragm, and maintaining the pressure during cooling to obtain the secondary composite film.
Soaking the obtained secondary composite membrane in water, continuously soaking for 8 hours at the temperature of 55 ℃, taking out the secondary composite membrane, uncovering the membrane to separate the melted and resolidified membrane together with the negative electrode active material layer from the copper foil, and removing the copper foil to obtain the negative electrode active material layer adhered with the membrane; transferring the anode active material layer adhered with the diaphragm into a ball milling tank, and mixing the anode active material layer with the diaphragm according to the mass ratio of 30:1 adding zirconia ball-milling beads, and ball-milling and mixing for 4 hours under the condition that the ball-milling rotating speed is 600r/min to obtain ball grinding materials; and transferring the ball-milled material into a carbonization furnace, pyrolyzing the ball-milled material at 1200 ℃ under the protection of nitrogen gas for 6 hours, cooling the ball-milled material to room temperature along with the furnace, and discharging the ball-milled material to finish the recovery of the graphite cathode of the lithium ion battery.
Example 4
The difference between this embodiment and embodiment 1 is that: the common heating is adopted to replace the flat heating, and specifically, no flat plate is used for carrying out hot pressing on the composite negative electrode plate in the heating process, and the rest conditions are kept unchanged.
Example 5
The difference between this embodiment and embodiment 1 is that: after the heating of the flat plate is stopped, the flat plate is removed while the flat plate is hot, the composite negative electrode plate is naturally cooled to the room temperature, and the rest conditions are kept unchanged.
The copper foil recovered in examples 1 to 5 was observed, and the surface residual anode active material was scraped, the weight m1 thereof was weighed, and the mass m2 of the recovered graphite anode material was then weighed, and the loss ratio=m1/(m1+m2) ×100% was calculated, and the specific results are shown in table 1:
TABLE 1 loss rate
In addition, in the recycling process, whether the phenomenon that the film cannot be continuously torn off is observed when each embodiment is recycled, specifically, in the film tearing process of embodiments 1-3, continuous film tearing can be successfully completed, in the film tearing process of embodiment 4, 6 times of breakage of a single battery core is required to be conducted again, but the film tearing process of embodiment 5 can be completed conveniently, and in the film tearing process of embodiment 5, 3 times of breakage of the single battery core is required to be conducted again.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (7)
1. The method for recycling the graphite cathode of the lithium ion battery is characterized by comprising the following steps of:
s1: disassembling the lithium ion battery, and removing the shell to obtain a bare cell; the bare cell comprises a positive pole piece, a negative pole piece and a diaphragm arranged between the positive pole piece and the negative pole piece;
s2: stripping the positive electrode plate, and reserving the negative electrode plate and the diaphragm to keep the positive electrode plate and the diaphragm in an adhesion state so as to obtain a composite negative electrode plate adhered with the diaphragm;
s3: tiling the composite negative electrode plate, keeping the composite negative electrode plate in a state that the negative electrode plate is positioned at the bottom and the diaphragm is positioned at the top of the negative electrode plate;
s4: heating the tiled composite negative electrode plate to completely melt the diaphragm, and then cooling to resolidify the melted diaphragm to obtain a secondary composite film;
s5: soaking the obtained secondary composite film in water, removing the film to separate the melted and resolidified diaphragm together with the negative electrode active material layer and the copper foil, and removing the copper foil to obtain the negative electrode active material layer adhered with the diaphragm; and then heating and pyrolyzing the lithium ion battery to carbonize the diaphragm, thus completing the recovery of the graphite cathode of the lithium ion battery.
2. The method according to claim 1, wherein in the step S4, the heating includes: and (3) adopting flat plate heating, pressing a heating plate on the surface of the diaphragm, and maintaining the pressure of 0.03-0.05MPa in the heating process.
3. The method according to claim 2, wherein in the step S4, the cooling includes: the plate heating is stopped, allowed to cool naturally, and the pressure is maintained during the cooling.
4. The method according to claim 1, wherein in the step S5, the thermal pyrolysis comprises: pyrolysis is carried out at 800-1200 ℃ under the protection of inert gas.
5. The method according to claim 1, wherein in the step S5, the separator-adhered anode active material layer is ball-milled and mixed before the thermal pyrolysis.
6. The method for recycling graphite negative electrode of lithium ion battery according to claim 5, wherein the ball milling mixing comprises: the mass ratio of the ball materials is 20:1-30:1 adding zirconia ball-milling beads, and ball-milling and mixing for 2-4 hours under the condition that the ball-milling rotating speed is 400-600r/min to obtain the ball grinding material.
7. The method for recycling graphite negative electrode of lithium ion battery according to claim 1, wherein the separator comprises a base film, and the base film is any one of a polypropylene base film and a polyethylene base film.
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