CN114006065B - Method for recycling ceramic diaphragm of waste lithium battery - Google Patents
Method for recycling ceramic diaphragm of waste lithium battery Download PDFInfo
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- CN114006065B CN114006065B CN202011522518.3A CN202011522518A CN114006065B CN 114006065 B CN114006065 B CN 114006065B CN 202011522518 A CN202011522518 A CN 202011522518A CN 114006065 B CN114006065 B CN 114006065B
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- 239000000919 ceramic Substances 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000002699 waste material Substances 0.000 title claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 18
- 238000004064 recycling Methods 0.000 title claims abstract description 12
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 42
- 239000012528 membrane Substances 0.000 claims abstract description 41
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 238000000498 ball milling Methods 0.000 claims abstract description 28
- 239000012535 impurity Substances 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 12
- 238000007599 discharging Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 8
- 239000011812 mixed powder Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 150000002739 metals Chemical class 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 28
- 239000004033 plastic Substances 0.000 claims description 10
- 229920003023 plastic Polymers 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 2
- 238000001238 wet grinding Methods 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims 1
- 239000000155 melt Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 20
- 238000000926 separation method Methods 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 6
- 238000000053 physical method Methods 0.000 abstract description 4
- 239000002585 base Substances 0.000 description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 238000002386 leaching Methods 0.000 description 8
- 239000007773 negative electrode material Substances 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 208000028659 discharge Diseases 0.000 description 4
- 238000007885 magnetic separation Methods 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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
- 239000012267 brine Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide 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
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Processing Of Solid Wastes (AREA)
- Secondary Cells (AREA)
Abstract
The utility model provides a method for recycling ceramic diaphragms of waste lithium batteries, and a bagThe method comprises the following steps: discharging the waste lithium ion battery, and separating out anode and cathode mixed powder, a battery shell and a ceramic diaphragm by a physical crushing method; immersing the separated ceramic membrane in water, stirring and cleaning, removing impurities adhered to the surface of the ceramic membrane, mixing the removed impurities with positive and negative electrode 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, then carrying out ultrasonic treatment to remove the residual ceramic layer on the surface of the diaphragm substrate, and then separating the ceramic material and the diaphragm substrate through density difference to obtain a ceramic material and a diaphragm substrate; the ceramic material is regenerated after heat treatment to obtain alpha-Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The membrane substrate is heated by an extruder, melted, extruded and granulated. The separation process of the utility model adopts a physical method, so that the ceramic layer and the membrane substrate on the membrane can be completely recovered, the wastewater discharge is less, the recovery cost of the membrane is greatly reduced, and the ecological environment is protected.
Description
Technical Field
The utility model belongs to the technical field of waste lithium ion battery recovery, and particularly relates to a method for recovering a waste lithium battery ceramic diaphragm.
Background
With the progress of new energy product technology, especially the demand of the electronic market and the electric vehicle market for lithium ion batteries is increasing year by year. By the end of 2017, 180 or more thousands of new energy automobiles are promoted in China, the assembled power battery is about 86.9GWh, and the lithium ion battery gradually enters a large-scale retirement period in 2018, so that the problem of lithium ion battery treatment is urgent.
At present, lithium ion battery recovery is mainly focused on copper foil, aluminum foil and aluminum foilThe recovery of nickel, cobalt, manganese and lithium resources is less related to the recovery of ceramic diaphragms, and the ceramic diaphragm recovery material mainly comprises alumina, polyolefin diaphragms and anode and cathode powder partially adhered to the surfaces of the diaphragms, if the recovery is not performed, the waste of the resources is caused, and the environment is easy to be polluted. Chinese patent No. 106299532A discloses a method for recovering ceramic membrane of lithium battery, which comprises mechanically pulverizing the discharged residual electric quantity of scrapped battery into 0.5-3cm fragments, separating the fragments into ceramic membrane in a flotation agent, burning the ceramic membrane in a high temperature furnace at 380-450deg.C, leaching aluminum element from the residue obtained by the burning, adding alkali liquor to precipitate Al (OH) 3 Finally Al (OH) 3 Heat treating at 140-150deg.C to obtain gamma-Al 2 O 3 . According to the method, only aluminum oxide is recycled, and the polyolefin diaphragm is directly burnt out, so that not only is the resource wasted, but also pollutants such as dioxin and the like are easily formed; meanwhile, the method consumes acid and alkali, and the amount of wastewater is large. Chinese patent No. 108110360A discloses a method for recovering alumina from waste lithium battery ceramic membrane, which comprises the steps of roasting the separated ceramic membrane through a muffle furnace at 150-300 ℃ to remove residual binder, leaching aluminum element with alkali liquor at 150-240 ℃, introducing carbon dioxide gas to generate precipitate, and finally calcining to obtain alumina powder. The alkali liquor leaching reprecipitation mode can not recover aluminum element by 100%, and the waste water amount is large. Chinese utility model CN205911385U and CN210586171U both disclose a ceramic membrane separation recovery device, respectively leaching aluminum element by alkali liquor and separating alumina from polyolefin membrane substrate by ultrasound. The problems of incomplete alumina removal and the like exist in both alkali liquor leaching recovery of aluminum element and a simple ultrasonic separation method.
Therefore, it is necessary to solve the above-described drawbacks of the prior art.
Disclosure of Invention
The utility model aims to overcome the defects of the prior art, and provides a method for recycling the ceramic diaphragm of the waste lithium battery, which enables the ceramic layer on the ceramic diaphragm to be completely separated from the diaphragm base material, has simple process, low cost and little wastewater discharge, and can realize industrial production.
The utility model provides a method for recycling a ceramic diaphragm of a waste lithium battery, which comprises the following steps:
discharging the waste lithium ion batteries, and separating out anode and cathode mixed powder, a battery shell and a ceramic diaphragm by a physical crushing and sorting method;
immersing the separated ceramic membrane in water, removing impurities adhered to the surface of the ceramic membrane through stirring and cleaning, and then mixing the removed solid impurities with positive and negative electrode powder to recover 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; then carrying out ultrasonic treatment on the diaphragm substrate, removing residual ceramic materials on the surface of the diaphragm substrate, and separating the ceramic materials from the diaphragm substrate through density difference;
the ceramic material is subjected to heat treatment and regenerated to obtain alpha-Al 2 O 3 ；
And (3) heating, melting, extruding and granulating the diaphragm base material through an extruder to obtain plastic particles.
The utility model has the following technical effects:
(1) According to the utility model, the ceramic diaphragm separated from the waste lithium battery is cleaned, impurities (mainly positive and negative electrode powder) adhered to the surface of the diaphragm are removed, the surface of the diaphragm is cleaned, and the recovery rate of positive and negative electrode materials is improved.
(2) The utility model adopts the heat treatment, ball milling and ultrasonic treatment modes to remove the ceramic layer of the diaphragm, and the whole separation process adopts a physical method, so that the ceramic layer on the diaphragm and the diaphragm substrate can be completely separated, 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 waste water discharge can be greatly reduced, the diaphragm recovery cost is greatly reduced, and the ecological environment is protected.
(3) According to the utility model, the muffle furnace heat treatment is adopted to regenerate alumina powder and the polyolefin diaphragm substrate are melted, extruded and re-granulated, so that the diaphragm is effectively reused.
(4) The utility model has simple process, short process flow and environmental protection, improves the resource recovery rate of the lithium battery, realizes the recycling of resources and is beneficial to industrialized mass production.
The method meets the current industrial requirements and has very wide application prospect.
Drawings
FIG. 1 is a flow chart of a method of an embodiment of the present utility model;
FIG. 2A is a state diagram of the front surface of a ceramic separator according to example 1 of the present utility model;
FIG. 2B is a surface state diagram of a ceramic separator treated according to example 1 of the present utility model;
FIG. 3 is an XRD pattern of alumina powder obtained by the treatment of example 1 of the present utility model.
Detailed Description
The present utility model will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present utility model more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the utility model.
Referring to fig. 1, the method for recycling the ceramic diaphragm of the waste lithium battery provided by the embodiment of the utility model comprises the following steps:
s1, discharging the waste lithium ion batteries, and separating out a positive and negative electrode mixed material, a battery shell and a ceramic diaphragm by a physical crushing and sorting method.
In the step, the waste lithium ion battery is firstly subjected to discharge treatment, which can be completed by adopting a brine soaking or charging and discharging machine mode, and then positive and negative electrode mixed powder, battery shell, copper foil, aluminum foil and ceramic diaphragm are automatically disassembled and separated through physical methods such as crushing, magnetic separation, screening and the like.
S2, immersing the separated ceramic membrane in water, removing impurities adhered to the surface of the ceramic membrane through stirring and cleaning, mixing the removed solid impurities with positive and negative electrode powder, and recovering valuable metals.
When the ceramic diaphragm is crushed and separated in the step S1, partial impurities still adhere to the surface, the impurities contain anode and cathode materials, the adhered impurities on the surface of the diaphragm can be removed rapidly and efficiently through stirring and cleaning treatment, and the impurities are led into an anode and cathode mixed powder recovery procedure to recover valuable elements. Thus, the surface of the diaphragm is cleaned, and the recovery rate of the anode material and the cathode material is improved.
Stirring and cleaning with stirring machine at stirring speed of 100-500rpm for 0.5-2 hr at normal temperature.
S3, sequentially carrying out heat treatment and ball milling treatment on the ceramic diaphragm subjected to stirring and cleaning to enable the ceramic material to fall off from the ceramic substrate; and then carrying out ultrasonic treatment to remove the residual ceramic material on the surface of the diaphragm substrate, and separating the ceramic material from the diaphragm substrate through density difference.
The method comprises the 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. The ceramic material is adhered to the diaphragm base material in the form of coating through the adhesive, so that the adhesive is softened and the diaphragm is slightly deformed through heat treatment, and then the ceramic diaphragm and ball mill balls are subjected to 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 separated, and the ceramic material is separated from the diaphragm base material. As the diaphragm base material is generally made of polyethylene or polypropylene plastic, the diaphragm base material is relatively high in toughness, and can not be deteriorated or agglomerated by heat treatment and wet ball milling at relatively low temperature, and the separated diaphragm base material can be recycled and then the plastic particles can be regenerated by heating and melting.
The step adopts a heat treatment and wet ball milling mode, the heat treatment temperature is 100-200 ℃, and the heat treatment time is 5-30min; the wet ball milling is water adding wet milling, the ball material mass ratio is 10-300:1, the rotation 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 treatment and powder removal (separation of the ceramic material coating and the diaphragm substrate) is subjected to ultrasonic treatment, so that the ceramic material coating remained on the ceramic substrate is removed, and the ceramic material and the diaphragm substrate are thoroughly separated. The ultrasonic treatment is carried out under the condition that the ultrasonic frequency is 25-130KHZ, the treatment time is 0.5-2h, and the temperature is normal temperature.
After the ceramic material coating is separated from the diaphragm base material, the diaphragm base material is made of polyethylene or polypropylene plastic, and the density is lower than that of water, so that the diaphragm base material can float on the water surface; while the ceramic material is alumina, which has a density much higher than that of water, and will sink into the water bottom. After the ultrasonic treatment is completed, the diaphragm substrate and the ceramic material are separated by the density difference of the diaphragm substrate and the ceramic material.
S4, regenerating the ceramic material through heat treatment to obtain alpha-Al 2 O 3 。
In the step, the separated ceramic material is subjected to heat treatment in a muffle furnace to remove the binder remained on the ceramic material, thus obtaining the alpha-Al with higher purity 2 O 3 。
Specifically, the heat treatment temperature is 300-500 ℃ and the time is 2-6h.
And S5, heating, melting, extruding and granulating the diaphragm base material through an extruder.
The separated diaphragm base material can be recycled as waste plastic, and is heated, melted, extruded and granulated by adopting an extruder at the temperature of 200-300 ℃ to obtain diaphragm base material plastic particles which are reused in other fields.
In the recovery process of the ceramic diaphragm of the waste lithium battery, the ceramic material coating on the diaphragm is removed by heat treatment and ball milling, and meanwhile, the ceramic material adhered to the surface of the diaphragm is completely separated from the diaphragm base material by deep cleaning and gravity separation in combination with ultrasonic treatment. Compared with the prior art, the utility model adopts a physical method in the whole separation process, so that the ceramic material and the membrane substrate on the membrane can be completely recovered, and the treatment by chemical methods such as acid leaching and alkali leaching is not needed, thereby not only reducing the recovery cost of the ceramic membrane, but also greatly reducing the discharge of wastewater and being beneficial to protecting ecological environment.
The present utility model will be described in further detail with reference to examples.
Example 1:
s1, firstly discharging a waste lithium ion battery in 5% NaCl saline solution for 24 hours, and then automatically disassembling the waste lithium ion battery by crushing, magnetic separation and screening methods to separate positive and negative electrode mixed powder, a battery shell, copper foil, aluminum foil and a ceramic diaphragm;
s2, immersing the separated ceramic membrane in water at the ambient temperature of 25 ℃, placing the ceramic membrane in a stirring and cleaning device, stirring at the speed of 200rpm for 1h, and removing impurities adhered to the surface of the ceramic membrane. Mixing the removed powder with positive and negative electrode materials, allowing the mixture to enter a positive and negative electrode material recovery process, and allowing the cleaned ceramic diaphragm to enter the next process;
s3, placing the ceramic diaphragm cleaned in the step S2 in a high-temperature oven at 150 ℃ at the ambient temperature of 25 ℃, performing heat treatment for 10min, and then loading the ceramic diaphragm material into ball milling equipment, wherein the ball milling rate is 800rpm, and performing ball milling treatment for 0.5h; then the materials are introduced into ultrasonic equipment and are subjected to ultrasonic treatment for 1 hour under the condition that the ultrasonic frequency is 40 KHZ; finally separating the membrane substrate and the ceramic material by density difference;
s4, putting the ceramic material obtained in the step S3 into a muffle furnace, performing heat treatment for 4 hours at 450 ℃ and regenerating to obtain alpha-Al 2 O 3 ；
S5, placing the diaphragm substrate obtained in the step S3 into an extruder, and carrying out melt extrusion granulation at the temperature of 250 ℃ to obtain plastic particles.
Referring to fig. 2A and 2B, it can be clearly seen by comparing the surface states of the ceramic membrane before and after treatment of the embodiment, the ceramic material layer on the surface of the membrane is thoroughly and cleanly separated from the membrane substrate by adopting the ceramic membrane treated by the utility model, and the recovery effect is good.
Referring to fig. 3, the ceramic material alumina recovered in this example is relatively pure, has good crystallinity, and has no impurity phase.
Example 2:
s1, discharging a waste lithium ion battery for about 4 hours (discharging for many times, ensuring the voltage of the battery to be lower than 1-2V) through a charging and discharging machine, and then automatically disassembling and separating positive and negative electrode mixed powder, a battery shell, copper foil, aluminum foil and a ceramic diaphragm through crushing, magnetic separation and screening methods;
s2, immersing the separated ceramic membrane in water at the ambient temperature of 25 ℃, placing the ceramic membrane in a stirring and cleaning device, stirring at the speed of 500rpm for 1h, and removing impurities adhered to the surface of the ceramic membrane. Mixing the removed powder with positive and negative electrode materials, allowing the mixture to enter a positive and negative electrode material recovery process, and allowing the cleaned ceramic diaphragm to enter the next process;
s3, placing the ceramic diaphragm cleaned in the step S2 in a high-temperature oven at 180 ℃ at the ambient temperature of 25 ℃, performing heat treatment for 10min, then loading the ceramic diaphragm material into ball milling equipment, wherein the ball milling rate is 1200rpm, and performing ball milling treatment for 1h; then the materials are introduced into ultrasonic equipment and are subjected to ultrasonic treatment for 2 hours under the condition that the ultrasonic frequency is 80 KHZ; finally separating the membrane substrate and the ceramic material by density difference;
s4, putting the ceramic material obtained in the step S3 into a muffle furnace, performing heat treatment at 350 ℃ for 6 hours, and regenerating to obtain alpha-Al 2 O 3 ；
And S5, placing the diaphragm substrate obtained in the step S3 into an extruder, and carrying out melt extrusion granulation at the temperature of 200 ℃ to obtain plastic particles.
Example 3:
s1, discharging a waste lithium ion battery for about 4 hours by adopting a charging and discharging machine (discharging for a plurality of times, ensuring the voltage of the battery to be lower than 1V), 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 methods;
s2, immersing the separated ceramic membrane in water at the ambient temperature of 25 ℃, placing the ceramic membrane in a stirring and cleaning device, stirring at the speed of 100rpm for 2 hours, and removing impurities adhered to the surface of the ceramic membrane. Mixing the removed powder with positive and negative electrode materials, allowing the mixture to enter a positive and negative electrode material recovery process, and allowing the cleaned ceramic diaphragm to enter the next process;
s3, placing the ceramic diaphragm cleaned in the step S2 in a high-temperature oven at 200 ℃ at an ambient temperature of 25 ℃, performing heat treatment for 5min, and then loading the ceramic diaphragm material into ball milling equipment, wherein the ball milling rate is 1200rpm, and performing ball milling treatment for 2h; then the materials are introduced into ultrasonic equipment and are subjected to ultrasonic treatment for 2 hours under the condition that the ultrasonic frequency is 80 KHZ; finally separating the membrane substrate and the ceramic material by density difference;
s4, putting the ceramic material obtained in the step S3 into a muffle furnace,heat treating at 500 deg.c for 2 hr to regenerate alpha-Al 2 O 3 ；
S5, placing the diaphragm substrate obtained in the step S3 into an extruder, and carrying out melt extrusion granulation at the temperature of 250 ℃ to obtain plastic particles.
The above-described embodiments of the present utility model are only some of the preferred embodiments of the present utility model and are not intended to limit the present utility model, and any modifications, equivalent substitutions and improvements made by those skilled in the art without departing from the spirit of the present utility model shall fall within the scope of the present utility model.
Claims (5)
1. The method for recycling the ceramic diaphragm of the waste lithium battery is characterized by comprising the following steps of:
discharging the waste lithium ion batteries, and separating out anode and cathode mixed powder, a battery shell and a ceramic diaphragm by a physical crushing and sorting method;
immersing the separated ceramic membrane in water, removing impurities adhered to the surface of the ceramic membrane through stirring and cleaning, and then mixing the removed solid impurities with positive and negative electrode powder to recover valuable metals;
softening the binder and slightly deforming the ceramic diaphragm through heat treatment of the cleaned ceramic diaphragm, and then generating collision, friction and shearing actions between the ceramic diaphragm and ball-milling beads through wet ball-milling treatment, so that the ceramic material coating adhered to the diaphragm substrate is separated from the ceramic substrate, and the ceramic material is separated from the diaphragm substrate; then carrying out ultrasonic treatment on the diaphragm substrate, removing residual ceramic materials on the surface of the diaphragm substrate, and separating the ceramic materials from the diaphragm substrate through density difference; the heat treatment temperature is 100-200 ℃, and the heat treatment time is 5-30min; the wet ball milling treatment is water-added wet milling, the ball material mass ratio 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;
the ceramic material is subjected to heat treatment and regenerated to obtain alpha-Al 2 O 3 ；
And (3) heating, melting, extruding and granulating the diaphragm base material through an extruder to obtain plastic particles.
2. The method for recycling the ceramic membrane of the waste lithium battery according to claim 1, wherein the time for removing the impurities adhered to the surface of the ceramic membrane by stirring and cleaning 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 according to claim 1, wherein the frequency of ultrasonic treatment after heat treatment and ball milling and powder removal of the ceramic diaphragm is 25-130KHZ, the treatment time is 0.5-2h, and the temperature is normal temperature.
4. The method for recycling the ceramic membrane of the waste lithium battery according to claim 1, wherein the heat treatment temperature of the ceramic material is 300-500 ℃ and the heat treatment time is 2-6h.
5. The method for recycling waste lithium battery ceramic diaphragms according to claim 1, wherein the melt extrusion granulation temperature of the diaphragm base material is 200-300 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011522518.3A CN114006065B (en) | 2020-12-22 | 2020-12-22 | Method for recycling ceramic diaphragm of waste lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011522518.3A CN114006065B (en) | 2020-12-22 | 2020-12-22 | Method for recycling ceramic diaphragm of waste lithium battery |
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| Publication Number | Publication Date |
|---|---|
| CN114006065A CN114006065A (en) | 2022-02-01 |
| CN114006065B true CN114006065B (en) | 2024-01-26 |
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| CN115663324B (en) * | 2022-08-05 | 2023-10-20 | 西安交通大学 | Retired battery diaphragm repairing and regenerating process |
| CN115832498B (en) * | 2022-11-24 | 2024-01-26 | 厦门海辰储能科技股份有限公司 | Recovery equipment and recovery method for battery electrode |
| CN116742181B (en) * | 2023-08-03 | 2024-04-05 | 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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