CN114006065A - Method for recovering ceramic diaphragm of waste lithium battery - Google Patents
Method for recovering ceramic diaphragm of waste lithium battery Download PDFInfo
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- CN114006065A CN114006065A CN202011522518.3A CN202011522518A CN114006065A CN 114006065 A CN114006065 A CN 114006065A CN 202011522518 A CN202011522518 A CN 202011522518A CN 114006065 A CN114006065 A CN 114006065A
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- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000002699 waste material Substances 0.000 title claims abstract description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 19
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 238000000498 ball milling Methods 0.000 claims abstract description 28
- 239000012535 impurity Substances 0.000 claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000007599 discharging Methods 0.000 claims abstract description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 11
- 239000011812 mixed powder Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
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- 238000004064 recycling Methods 0.000 claims description 9
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- 238000001125 extrusion Methods 0.000 claims description 4
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- 239000007787 solid Substances 0.000 claims description 3
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 208000028659 discharge Diseases 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000007885 magnetic separation Methods 0.000 description 4
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- -1 polyethylene Polymers 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
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- 239000010406 cathode material Substances 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
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- 230000005484 gravity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000010299 mechanically pulverizing process Methods 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
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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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
-
- 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 provides a method for recovering a ceramic diaphragm of a waste lithium battery, which comprises the following steps: discharging the waste lithium ion battery, and separating out positive and negative mixed powder, a battery shell and a ceramic diaphragm by a physical crushing method; immersing the separated ceramic diaphragm into water, stirring and cleaning, removing impurities adhered to the surface of the ceramic diaphragm, mixing the removed impurities with the anode and cathode powder, and recovering valuable metals; sequentially carrying out heat treatment and ball milling treatment on the cleaned diaphragm to enable the ceramic layer to fall off from the ceramic substrate, carrying out ultrasonic treatment to remove the residual ceramic layer on the surface of the diaphragm substrate, and then separating by density difference to obtain a ceramic material and the diaphragm substrate; regenerating the ceramic material after heat treatment to obtain alpha-Al2O3(ii) a Heating, melting, extruding and granulating the diaphragm base material through an extruder. The separation process of the invention adopts a physical method, so that the ceramic layer on the diaphragm and the diaphragm substrate can be completely recovered, the waste water discharge is less, the recovery cost of the diaphragm is greatly reduced, and the ecological environment is protected.
Description
Technical Field
The invention belongs to the technical field of waste lithium ion battery recovery, and particularly relates to a method for recovering a waste lithium ion battery ceramic diaphragm.
Background
With the progress of new energy product technology, the demand of lithium ion batteries in the electronic market and the electric vehicle market in particular is increasing year by year. By the end of 2017, more than 180 new energy vehicles are cumulatively popularized in China, the power battery is assembled by about 86.9GWh, the lithium ion battery gradually enters a large-scale retirement period since 2018, and the problem of lithium ion battery treatment is imminent.
At present, the recovery of lithium ion batteries is mainly concentrated on the recovery of copper foil, aluminum foil and nickel, cobalt, manganese and lithium resources, and less relates to the recovery of ceramic diaphragms, and the ceramic diaphragm recovery material mainly contains alumina, polyolefin diaphragms and anode and cathode powder materials partially adhered to the surfaces of the diaphragms, so that if the recovery is not carried out, the resource waste is caused, and the environment is easily polluted. Chinese patent CN106299532A discloses a method for recovering ceramic diaphragm of lithium battery, which comprises discharging residual electricity of discarded battery, mechanically pulverizing into 0.5-3cm fragments, placing the fragments into a flotation agent to separate out ceramic diaphragm, firing the ceramic diaphragm in a high temperature furnace at 380 deg.C and 450 deg.C, acid leaching the residue obtained by firing to obtain aluminum element, adding alkali liquor to precipitate Al (OH)3Finally, Al (OH)3Heat treatment at 140-150 deg.C to obtain gamma-Al2O3. The method only recovers the alumina, and the polyolefin diaphragm is directly burnt, thereby not only causing resource waste, but also easily forming pollutants such as dioxin and the like; meanwhile, the method consumes acid and alkali and has large amount of waste water. Chinese invention patent CN108110360A discloses a method for recovering alumina in ceramic diaphragms of waste lithium batteries, which comprises the steps of roasting the separated ceramic diaphragms at 300 ℃ through a muffle furnace at 150-And finally, calcining to obtain the alumina powder. The alkaline solution leaching and reprecipitation mode can not recover 100% of aluminum element, and the waste water amount is large. Chinese utility model CN205911385U and CN210586171U both disclose a ceramic diaphragm separation recovery unit, which respectively leaches aluminum element through alkali liquor and separates alumina and polyolefin diaphragm base material through ultrasound. The problems of incomplete removal of alumina and the like exist in alkali liquor leaching and aluminum element recovery and a simple ultrasonic separation method.
Therefore, there is a need to address the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for recovering a ceramic diaphragm of a waste lithium battery, so that a ceramic layer on the ceramic diaphragm is completely separated from a diaphragm substrate, the process is simple, the cost is low, the waste water discharge is less, and the industrial production can be realized.
The invention provides a method for recovering a ceramic diaphragm of a waste lithium battery, which comprises the following steps:
discharging the waste lithium ion battery, and separating out positive and negative electrode mixed powder, a battery shell and a ceramic diaphragm by a physical crushing and sorting method;
immersing the separated ceramic diaphragm into water, removing impurities adhered to the surface of the ceramic diaphragm through stirring and cleaning, mixing the removed solid impurities with the anode and cathode powder, and recovering valuable metals;
sequentially carrying out heat treatment and ball milling treatment on the cleaned ceramic diaphragm to enable the ceramic material to fall off from the ceramic substrate; carrying out ultrasonic treatment on the diaphragm substrate to remove residual ceramic materials on the surface of the diaphragm substrate, and then separating the ceramic materials from the diaphragm substrate through density difference;
the ceramic material is regenerated to obtain alpha-Al through heat treatment2O3；
Heating, melting, extruding and granulating the diaphragm base material through an extruder to obtain plastic granules.
The invention has the following technical effects:
(1) according to the invention, the ceramic diaphragm separated from the waste lithium battery is cleaned, impurities (mainly anode and cathode powder) adhered to the surface of the diaphragm are removed, the surface of the diaphragm is cleaned, and the recovery rate of the anode and cathode materials is improved.
(2) The ceramic layer of the diaphragm is removed by adopting heat treatment, ball milling and ultrasonic treatment, the ceramic layer on the diaphragm and the diaphragm substrate can be completely separated by adopting a physical method in the whole separation process, the treatment method is simple and efficient, the removal efficiency is high, chemical treatment methods such as acid and alkali leaching are not needed, the discharge of waste water can be greatly reduced, the recovery cost of the diaphragm is greatly reduced, and the ecological environment is protected.
(3) The invention adopts muffle furnace heat treatment to regenerate alumina powder and polyolefin diaphragm base material to melt, extrude and re-granulate, so that the diaphragm can be effectively reused.
(4) The method has the advantages of simple process, short process flow, environmental protection, improvement of the resource recovery rate of the lithium battery, realization of the cyclic utilization of resources and contribution to industrial large-scale production.
The method of the invention meets the requirements of the current industry and has very wide application prospect.
Drawings
FIG. 1 is a flow chart of a method of an embodiment of the present invention;
FIG. 2A is a view showing a state of a surface of a ceramic separator before treatment in example 1 of the present invention;
FIG. 2B is a view showing a surface state of the ceramic separator after treatment according to example 1 of the present invention;
FIG. 3 is an XRD pattern of the alumina powder obtained by the treatment of example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, the method for recovering a ceramic diaphragm of a waste lithium battery provided by the embodiment of the invention comprises the following steps:
s1, discharging the waste lithium ion battery, and separating the mixed material of the positive electrode and the negative electrode, the battery shell and the ceramic diaphragm by a physical crushing and sorting method.
In the step, the waste lithium ion battery is subjected to discharge treatment, the discharge treatment can be completed by adopting a saline solution soaking or charging and discharging machine mode, and then positive and negative mixed powder, a battery shell, copper foil, aluminum foil and a ceramic diaphragm are automatically disassembled and separated by physical methods such as crushing, magnetic separation, screening and the like.
S2, immersing the separated ceramic diaphragm into water, removing impurities adhered to the surface of the ceramic diaphragm through stirring and cleaning, mixing the removed solid impurities with the anode and cathode powder, and recovering valuable metals.
When the ceramic diaphragm is broken and separated in the step S1, partial impurities still adhere to the surface of the ceramic diaphragm, the impurities comprise anode and cathode materials, the impurities adhered to the surface of the ceramic diaphragm can be quickly and efficiently removed through stirring and cleaning, the impurities are led into a process for recovering anode and cathode mixed powder, and valuable elements in the impurities are recovered. Therefore, the surface of the diaphragm is cleaned, and the recovery rate of the anode and cathode materials is improved.
The stirring speed of the stirrer adopted in the stirring and cleaning treatment is 100-500rpm, the treatment time is 0.5-2h, and the treatment is carried out at normal temperature.
S3, the ceramic diaphragm after being stirred and cleaned is subjected to heat treatment and ball milling treatment in sequence, so that the ceramic material falls off from the ceramic substrate; and then ultrasonic treatment is carried out to remove residual ceramic materials on the surface of the diaphragm substrate, and then the ceramic materials and the diaphragm substrate are separated through density difference.
The method comprises the following steps of firstly, adopting a heat treatment and ball milling method to enable the ceramic material coating on the surface of the diaphragm to fall off from the diaphragm substrate. Because the ceramic material is adhered to the diaphragm base material in a coating form through the adhesive, the adhesive is softened and the diaphragm is slightly deformed through heat treatment, and then the ceramic diaphragm and the ball-milling beads generate collision, friction, shearing and other actions through wet ball-milling treatment, so that the ceramic material coating adhered to the diaphragm base material can be quickly peeled off, and the ceramic material is separated from the diaphragm base material. Because the diaphragm base material is generally made of polyethylene or polypropylene plastic, the toughness is higher, the diaphragm base material is not deteriorated or agglomerated by heat treatment and wet ball milling at lower temperature, and the separated diaphragm base material can be heated and melted to reproduce plastic particles after being recovered.
The step adopts a heat treatment and wet ball milling mode, the heat treatment temperature is 100-; the wet ball milling is water wet milling, the mass ratio of ball materials is 10-300:1, the rotating speed of the ball mill is 500-1500rpm, the ball milling time is 0.5-4h, and the ball milling temperature is normal temperature.
In order to thoroughly remove the ceramic material on the diaphragm substrate, the diaphragm substrate material subjected to ball milling and powder removal (separation of the ceramic material coating from the diaphragm substrate) is subjected to ultrasonic treatment to remove the residual ceramic material coating on the ceramic substrate, so that the ceramic material and the diaphragm substrate are thoroughly separated. The ultrasonic treatment is carried out at ultrasonic frequency of 25-130KHZ for 0.5-2h at normal temperature.
After the ceramic material coating is separated from the diaphragm base material, the diaphragm base material is polyethylene or polypropylene plastic, and the density of the diaphragm base material is lower than that of water, so that the diaphragm base material can float on the water surface; the ceramic material is alumina, the density of which is far higher than that of water, and the ceramic material can sink to the water bottom. And after the ultrasonic treatment is finished, separating the diaphragm substrate from the ceramic material through the density difference between the diaphragm substrate and the ceramic material.
S4, carrying out heat treatment on the ceramic material, and regenerating to obtain alpha-Al2O3。
In the step, the separated ceramic material is subjected to muffle furnace heat treatment to remove the binder remained on the ceramic material, so that the alpha-Al with high purity can be obtained2O3。
Specifically, the heat treatment temperature is 300-500 ℃, and the time is 2-6 h.
S5, heating the diaphragm base material through an extruder, melting, extruding and granulating.
The separated diaphragm base material can be recycled as waste plastics, and is heated, melted, extruded and granulated by an extruder at the temperature of 200-300 ℃ to obtain diaphragm base material plastic particles, and the diaphragm base material plastic particles are applied to other fields again.
In the process of recovering the ceramic diaphragm of the waste lithium battery, the ceramic material coating on the diaphragm is peeled off in a heat treatment and ball milling mode, and the ceramic material adhered to the surface of the diaphragm is completely separated from the diaphragm substrate by combining deep cleaning and gravity separation in an ultrasonic treatment mode. Compared with the prior art, the method disclosed by the invention has the advantages that the ceramic material and the diaphragm base material on the diaphragm can be completely recovered by adopting a physical method in the whole separation process, and chemical methods such as acid leaching and alkali leaching are not required to be used for treatment, so that the recovery cost of the ceramic diaphragm is reduced, the discharge of waste water is greatly reduced, and the ecological environment is protected.
The present invention will be described in further detail with reference to examples.
Example 1:
s1, discharging the waste lithium ion battery in a 5% NaCl salt water solution for 24h, then automatically disassembling the waste lithium ion battery by crushing, magnetic separation and screening to separate out positive and negative mixed powder, a battery shell, copper foil, aluminum foil and a ceramic diaphragm;
s2 at 25 deg.C, immersing the separated ceramic membrane in water, placing in stirring cleaning equipment, stirring at 200rpm for 1h, and removing the impurities adhered on the surface of the ceramic membrane. Mixing the removed powder with positive and negative electrode materials, recycling the positive and negative electrode materials, and carrying out the next working procedure on the cleaned ceramic diaphragm;
s3, placing the ceramic diaphragm cleaned in the step S2 in a high-temperature oven at 150 ℃ at the environment temperature of 25 ℃, carrying out heat treatment for 10min, then loading the ceramic diaphragm material into ball milling equipment, wherein the mass ratio of ball to material is 100:1, the ball milling speed is 800rpm, and the ball milling treatment is carried out for 0.5 h; then introducing the material into ultrasonic equipment, and carrying out ultrasonic treatment for 1h under the condition that the ultrasonic frequency is 40 KHZ; finally separating the diaphragm substrate and the ceramic material through density difference;
s4 the ceramic material obtained in the step S3 is put into a muffle furnace, and is thermally treated for 4 hours at the temperature of 450 ℃ to regenerate the ceramic material to obtain alpha-Al2O3；
S5, placing the diaphragm base material obtained in the step S3 in an extruder, and performing melt extrusion granulation at the temperature of 250 ℃ to obtain plastic granules.
Referring to fig. 2A and fig. 2B, it can be clearly seen from the comparison of the states of the front and rear surfaces of the ceramic diaphragm processed in the embodiment of the present invention that, with the ceramic diaphragm processed according to the present invention, the ceramic material layer on the surface of the diaphragm is completely and cleanly separated from the diaphragm substrate, the removal rate is high, and the recovery effect is good.
Referring to fig. 3, the alumina of the ceramic material recovered in this example is pure, has good crystallinity and no impurity phase.
Example 2:
s1, discharging the waste lithium ion battery for about 4 hours by a charging and discharging machine (discharging for multiple times to ensure that the voltage of the battery is lower than 1-2V), and then automatically disassembling and separating positive and negative mixed powder, a battery shell, copper foil, aluminum foil and a ceramic diaphragm by crushing, magnetic separation and screening;
s2, at the ambient temperature of 25 ℃, the separated ceramic diaphragm is immersed in water, placed in stirring and cleaning equipment, and stirred at the speed of 500rpm for 1h to remove the impurities adhered to the surface of the ceramic diaphragm. Mixing the removed powder with positive and negative electrode materials, recycling the positive and negative electrode materials, and carrying out the next working procedure on the cleaned ceramic diaphragm;
s3, placing the ceramic diaphragm cleaned in the step S2 in a high-temperature oven at 180 ℃ at the environment temperature of 25 ℃, carrying out heat treatment for 10min, then loading the ceramic diaphragm material into ball milling equipment, wherein the mass ratio of ball to material is 50:1, the ball milling speed is 1200rpm, and the ball milling treatment is carried out for 1 h; then introducing the material into ultrasonic equipment, and carrying out ultrasonic treatment for 2h under the condition that the ultrasonic frequency is 80 KHZ; finally separating the diaphragm substrate and the ceramic material through density difference;
s4 the ceramic material obtained in the step S3 is put into a muffle furnace, heat treatment is carried out for 6 hours at the temperature of 350 ℃, and alpha-Al is obtained by regeneration2O3；
S5, placing the diaphragm base material obtained in the step S3 in an extruder, and performing melt extrusion granulation at the temperature of 200 ℃ to obtain plastic granules.
Example 3:
s1, discharging the waste lithium ion battery for about 4h by a charging and discharging machine (discharging for multiple times to ensure that the voltage of the battery is lower than 1V), and then automatically disassembling and separating the positive and negative mixed powder, the battery shell, the copper foil, the aluminum foil and the ceramic diaphragm by crushing, magnetic separation and screening;
s2 at 25 deg.C, immersing the separated ceramic membrane in water, placing in stirring cleaning equipment, stirring at 100rpm for 2h, and removing the impurities adhered on the surface of the ceramic membrane. Mixing the removed powder with positive and negative electrode materials, recycling the positive and negative electrode materials, and carrying out the next working procedure on the cleaned ceramic diaphragm;
s3, placing the ceramic diaphragm cleaned in the step S2 in a high-temperature oven at the temperature of 200 ℃ at the environment temperature of 25 ℃, carrying out heat treatment for 5min, then loading the ceramic diaphragm material into ball milling equipment, wherein the mass ratio of ball materials is 20:1, the ball milling speed is 1200rpm, and the ball milling treatment is carried out for 2 h; then introducing the material into ultrasonic equipment, and carrying out ultrasonic treatment for 2h under the condition that the ultrasonic frequency is 80 KHZ; finally separating the diaphragm substrate and the ceramic material through density difference;
s4, putting the ceramic material obtained in the step S3 into a muffle furnace, carrying out heat treatment for 2 hours at 500 ℃, and regenerating to obtain alpha-Al2O3；
S5, placing the diaphragm base material obtained in the step S3 in an extruder, and performing melt extrusion granulation at the temperature of 250 ℃ to obtain plastic granules.
The above-described embodiments of the present invention are merely exemplary and not intended to limit the present invention, and those skilled in the art may make various modifications, substitutions and improvements without departing from the spirit of the present invention.
Claims (7)
1. The method for recovering the ceramic diaphragm of the waste lithium battery is characterized by comprising the following steps of:
discharging the waste lithium ion battery, and separating out positive and negative electrode mixed powder, a battery shell and a ceramic diaphragm by a physical crushing and sorting method;
immersing the separated ceramic diaphragm into water, removing impurities adhered to the surface of the ceramic diaphragm through stirring and cleaning, mixing the removed solid impurities with the anode and cathode powder, and recovering valuable metals;
sequentially carrying out heat treatment and ball milling treatment on the cleaned ceramic diaphragm to enable the ceramic material to fall off from the ceramic substrate; carrying out ultrasonic treatment on the diaphragm substrate to remove residual ceramic materials on the surface of the diaphragm substrate, and then separating the ceramic materials from the diaphragm substrate through density difference;
the ceramic material is regenerated to obtain alpha-Al through heat treatment2O3；
Heating, melting, extruding and granulating the diaphragm base material through an extruder to obtain plastic granules.
2. The method for recycling the ceramic diaphragm of the waste lithium battery as claimed in claim 1, wherein the time for removing the impurities adhered on the surface of the ceramic diaphragm by stirring and cleaning treatment is 0.5-2h, the stirring speed is 100-500rpm, and the temperature is normal temperature.
3. The method for recycling the ceramic diaphragm of the waste lithium battery as claimed in claim 1, wherein the temperature of the ceramic diaphragm during the heat treatment is 100-200 ℃, and the heat treatment time is 5-30 min.
4. The method for recycling the ceramic diaphragm of the waste lithium battery as claimed in claim 1 or 3, wherein the ceramic diaphragm is wet-milled by adding water during ball milling treatment, the mass ratio of ball materials is 10-300:1, the ball milling rotation speed is 500-1500rpm, the ball milling time is 0.5-4h, and the temperature is normal temperature.
5. The method for recycling the ceramic diaphragm of the waste lithium battery as claimed in claim 4, wherein the frequency of the ultrasonic treatment after the heat treatment and the ball milling and the powder removal of the ceramic diaphragm is 25-130KHZ, the treatment time is 0.5-2h, and the temperature is normal temperature.
6. The method for recycling the ceramic diaphragm of the waste lithium battery as recited in claim 1, wherein the heat treatment temperature of the ceramic material is 300-500 ℃ and the heat treatment time is 2-6 h.
7. The method for recycling the ceramic diaphragm of the waste lithium battery as claimed in claim 1, wherein the melt extrusion granulation temperature of the diaphragm substrate is 200-300 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115663324A (en) * | 2022-08-05 | 2023-01-31 | 西安交通大学 | Restoration and regeneration process for retired battery diaphragm |
| CN115832498A (en) * | 2022-11-24 | 2023-03-21 | 厦门海辰储能科技股份有限公司 | Recovery equipment and recovery method for battery electrode |
| CN116742181A (en) * | 2023-08-03 | 2023-09-12 | 四川华洁嘉业环保科技有限责任公司 | Recycling method of lithium secondary battery diaphragm |
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