CN101984516A - Lithium ion battery resource recovery method for mobile phones - Google Patents
Lithium ion battery resource recovery method for mobile phones Download PDFInfo
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- CN101984516A CN101984516A CN2010102632277A CN201010263227A CN101984516A CN 101984516 A CN101984516 A CN 101984516A CN 2010102632277 A CN2010102632277 A CN 2010102632277A CN 201010263227 A CN201010263227 A CN 201010263227A CN 101984516 A CN101984516 A CN 101984516A
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to the technical field of resource recovery of solid battery. The method of the invention comprises the following steps: 1) sterilizing batteries; 2) carrying out sequencing and classification on the batteries; 3) discharging remaining power of the batteries; 4) cutting the shells of the batteries; 5) disassembling the batteries and sorting out components thereof; 6) peeling off active materials of the batteries; and 7) absorbing organic electrolyte. The method of the invention not only solves the problem of potential safety hazards resulting from entire breakage of the batteries and increased difficulty in sorting out the components of the batteries but also avoids high energy consumption and secondary environmental pollution caused by the commonly applied thermometallurgy method; and in addition, the method features safety, reliability, simple operation and low investment cost, and realizes comprehensive recovery of waste and old lithium ion batteries of mobile phones.
Description
Technical field
The present invention relates to the resource recovery technology field of solid state battery.
Background technology
In solid waste, waste mobile phone specialized lithium ion battery belongs to a more special class, and its particularity mainly shows: (1) amount is big and gather way swift and violent; (2) recovery value is higher; (3) potential environmental hazard does not obtain its people as yet and fully realizes.According to national the Ministry of Industry and Information Technology statistics, by the end of the year 2008, China cellphone subscriber reaches 6.4 hundred million approximately.The useful life of mobile phone specialized lithium ion battery is about 2 ~ 3 years, on average is equipped with two batteries by each mobile phone and calculates, and annual China produces about 400,000,000 waste mobile phone specialized lithium ion batteries at least, surpasses 6000 tons, and learies is also increasing substantially year by year.Contain chemical substances such as cobalt lithium oxide, lithium hexafluoro phosphate, organic carbonate, carbon materials, copper, aluminium in the lithium ion battery, wherein metallic cobalt accounts for 15%, copper 14%, aluminium 30%, lithium 0.1%.Cobalt and lithium belong to scarce resource, have recovery value.On the other hand, if can not effectively dispose, must cause serious environmental to pollute to a large amount of solid electronic refuse like this.Wherein, generally the positive pole material of lithium cobalt acid of Shi Yonging can cause human body skin allergy and PUD D, and burning is handled also can produce toxic gas.Lithium hexafluoro phosphate has severe corrosive, meets the water capacity and easily decomposes generation has extremely strong corrosiveness to skeleton HF; Also easy and strong oxidizer reacts; Burning produces P
2O
5Organic substance with difficult degradation.Organic carbonate has volatility, and is inflammable, causes people's sense of discomfort.So the waste mobile phone lithium ion battery is not only caused the huge waste of resource if can not rationally dispose, and also environment is caused severe contamination, and the ecosystem is produced harm.
At the waste mobile phone lithium ion battery, at present both at home and abroad main what adopt is pyrometallurgical method and process that physical separation-chemical lixiviation process matches.Foreign literature ((a) Kudo Mitsuhiko, Shimizu Sei.Deactivating method of used lithium cobalt secondary battery and cobalt recovering method from used lithium-cobalt secondary battery using the method[P] .JP, 10223264.1998-08-21; (b) Watanabe Tsutomu, Sugiya Tadashi, Sano Natsuhiro.Extract and recovering method for valuable metal from waste lithium battery[P] .JP, 10237419.1998-09-08.) the relatively typical handling process of report is successively: battery machine fragmentation (have with discharge mode), magnetic separation and/or impurity, extraction or electrolytic recovery cobalts such as gravity screening metal, sulfuric acid and hydrogen peroxide copper removal aluminium, reclaim lithiums.OnTo president Technology Shi Diwen E Si Lupu adopts " supercritical fluid is removed electrolytical system and method from energy storage and/or switching device ", and technological process is: artificial screening is also rejected atypical battery, the discharge of sodium bicarbonate water logging bubble, supercritical extract and is discharged electrolyte, disintegrating machine and stir and wash crusher machine, collect plastics, collect metal fillings (steel, aluminium, copper, gold etc.), passive electrode material powder.The core link of this technology is to adopt the organic electrolyte that contains the electrolyte lithium hexafluoro phosphate in the supercritical extraction method extraction battery, purpose is to guarantee that safety makes as much as possible the obtaining of electrolyte reclaim with there is no leakage, the recovery to other materials causes obstacle in the subsequent handling to avoid, and reduces the harmful components in institute's salvage material.The other technologies link is with existing technology is identical substantially both at home and abroad.The treatment process of being reported concentrates on the recovery of metallic cobalt and lithium mostly, does not consider the comprehensive recovery of battery resource.Simultaneously, it is broken usually battery to be carried out integral body in the technology, and this operation makes that the separating difficulty of each component strengthens greatly in the battery, the also corresponding equipment investment cost that increased.
Domestic processing method to waste and old lithium ion battery is similar with external technology, and is general earlier with battery burning (or roasting), removes organic substance; Screening obtains each metalloid; Powder under will sieving again is dissolved in the acid, regulates the pH purification and impurity removal, with the precipitation method, extraction, electrolysis separating and recovering cobalt and lithium.Do not consider the potential hazard of battery remaining capacity in the technology, do not consider problems such as environment that the electrolyte in the battery produces and safety hazard yet in processing bringing in the processing procedure.Simultaneously, the comprehensive utilization degree of resource is lower, and secondary environmental pollution is bigger.
The waste mobile phone lithium ion battery is a meticulous assembly that is made of multiple material, volume is small and exquisite, the present patent application is not to produce or to avoid producing secondary environmental pollution, to guarantee that safety in production is a prerequisite, adopt the machine cuts battery case, different assemblies such as letter sorting aluminium foil, copper core, battery case, adopt ultrasonic wave to peel off both positive and negative polarity active material on aluminium foil and the copper core respectively again, directly obtain pure aluminium foil, Copper Foil and battery case metal and relative single positive and negative utmost point active material.Select for use activated carbon organic exhaust gas adsorption plant to absorb the electrolyte bath that the manual volatility of disassembling in the process to be discharged of battery contains lithium hexafluoro phosphate, contain the lithium hexafluoro phosphate electrolyte bath with steaming slide method recovery active carbon adsorption function and recovery; Adopt Wet-process metallurgy method to reclaim metallic cobalt and lithium in the positive and negative electrode active material respectively again.
Summary of the invention
The object of the invention is exactly the problem of the potential potential safety hazard that causes and each component separating difficulty increasing of battery of thereupon causing in order to solve the cell integrated fragmentation that present both at home and abroad institute extensively adopts, and a kind of mobile phone lithium ion battery its recovery method as resource is provided.Adopt method of the present invention, not only solved the problem that caused potential safety hazard of cell integrated fragmentation and battery components letter sorting difficulty strengthens, the present high energy consumption that pyrometallurgical method caused that generally adopts and the problem of secondary environmental pollution have also been avoided simultaneously, safe and reliable, simple to operate, cost of investment is low, has realized the comprehensive recovery of waste mobile phone lithium-ion electric Pooled resources.
For reaching above-mentioned purpose, the technical scheme that the present invention takes is as follows:
A kind of mobile phone lithium ion battery its recovery method as resource, the method includes the steps of: 1) battery sterilization; 2) battery ordering arrangement; 3) the surplus discharge of electricity of battery; 4) battery case cutting; 5) battery is disassembled with assembly and is sorted; 6) electrode active material is peeled off; 7) absorption of organic electrolyte.
Because of the raw material waste mobile phone specialized lithium ion battery from different channels may carry various bacteriums or virus, so, at first to sterilize, sterilize it.The ozonization case that the present patent application preferably adopts the convection current of gas forced circulation to waste mobile phone specialized lithium ion battery sterilize, sterilization and deodorizing.
Step 3) is that the surplus electricity to battery discharges, and preferred scheme is the battery after the sterilization to be put into the conductive discharge case discharge residual electric energy.The discharge tank battery fixing structure is adjustable, to adapt to different batteries.This method is safe and reliable, has both made things convenient for Mechanical Method to disassemble, and has kept the recovery quality of each useful materials in the battery again.Preferred scheme is to remove the wiring board and the plastic bottom cover of battery before battery is put into the conductive discharge case, thereby make battery expose the discharge that both positive and negative polarity is convenient to battery.
Step 5) is disassembled and the assembly letter sorting battery, collects the assembly that comprises recyclable utilizations such as metal shell, aluminium foil, Copper Foil respectively.
Step 6) is carried out ultrasonic peeling off to above-mentioned steps 5 collected Copper Foils by ultrasonic wave, to peel off the electrode active material that applies on the Copper Foil; Adopt appropriate organic solvent to soak to collected aluminium foil, to separate the electrode active material that applies on the aluminium foil.As long as the organic solvent that uses can be isolated the electrode active material that applies on the aluminium foil, preferred N-methyl pyrrolidone.Peel off aluminium foil and the Copper Foil water cleaning again behind the electrode active material, can directly obtain pure aluminium foil and Copper Foil.The positive and negative electrode active material that strips down is the toner powder darkly, major part is deposited in the bottom of container, collect afterwash, separation, oven dry, reclaim metallic cobalt and lithium respectively by this area Wet-process metallurgy method commonly used at last, thereby realize comprehensive recovery all resources in the waste mobile phone specialized lithium ion battery.The supersonic generator of the preferred 1800W of supersonic generator, side position ultrasonic head.
Step 7) is that the volatility organic electrolyte is absorbed.For keeping the nontoxic cleaning of operational environment, battery case cutting and battery are disassembled all and are carried out in the fume hood of exhaust system is installed, and the ethene carbonic acid lipid volatility organic electrolyte that battery cuts and disassembles in the process to be discharged enters the active carbon respiratory box by exhaust duct and absorbs.
Above-mentioned mobile phone lithium ion battery its recovery method as resource, preferable scheme are also to carry out disinfection by ultraviolet light before the surplus discharge of electricity of the battery of step 3).Optimal scheme is the double-deck up and down configuration quartz burner at netted stainless steel conveyer belt, guarantees the pasteurised completely of battery, and the transfer rate of the conveyer belt that disinfecting time can be by regulating cell is controlled, and generally is controlled at 0.1-0.5m/min.
Above-mentioned mobile phone lithium ion battery its recovery method as resource, preferable scheme is in step 2) battery ordering arrangement before classify by the size specification of battery, and choose the bulge battery.
Beneficial effect of the present invention:
The said waste mobile phone specialized lithium of the present invention ion battery resource comprehensive recovery method, compare with the technology that generally includes flow processs such as " cell integrated fragmentation ", " pyrometallurgical method recovery metal " both at home and abroad at present:
(1) this method has been because of having evaded " cell integrated fragmentation " sport technique segment, thereby evaded the caused potential safety hazard of cell integrated fragmentation that extensively adopts at present both at home and abroad, greatly reduced the difficulty that each component of battery of causing is thus separated simultaneously;
(2) this method can directly obtain pure metal shell, aluminium foil and Copper Foil because of having evaded " pyrometallurgical method recovery metal " sport technique segment, has avoided the high energy consumption that causes thus and the problem of secondary environmental pollution;
(3) the inventive method adopts the absorption of charcoal absorption case to contain the electrolytical organic electrolyte of lithium hexafluoro phosphate, simple to operate, (CN ZL038020734) compares, and equipment investment cost is little a lot of to adopt the electrolytical method of supercritical extract device processes with Shi Diwen E Si Lupu;
(4) each operating procedure of the inventive method is simple, safe and reliable, has realized the comprehensive recovery of waste mobile phone lithium-ion electric Pooled resources.
Description of drawings
Specify the operating procedure of the inventive method below in conjunction with accompanying drawing 1:
Fig. 1 is the schematic flow sheet of its recovery method as resource of the said mobile phone specialized lithium of the present invention ion battery
Embodiment
Embodiment 1
As shown in Figure 1, the inventive method comprises 9 technical steps: battery sterilization, cell classification, battery ordering arrangement, battery disinfection by ultraviolet light, the surplus discharge of electricity of battery, battery case cut, battery is disassembled peels off with assembly letter sorting, electrode active material, organic electrolyte absorbs.
(1) sterilize, sterilize, the ozonization case of the indoor using gases forced circulation of ozone sterilization convection current in the ozone sterilization chamber that at first the waste mobile phone specialized lithium ion battery raw material of separate sources is transported into sealing.Processing time or/and the kind of virus is decided with the amount of carrying, generally needs 15-30min according to entrained bacterium;
(2) battery after will sterilizing, sterilizing is placed on manual sorting's platform the size specification by battery classifies, and chooses the bulge battery;
(3) with the battery of onesize specification, put in the hopper of collator, to the arrangement of sorting of the battery of chaotic, the speed that can come regulating cell to enter the disinfection by ultraviolet light line by the frequency button of regulating collator is not so that battery can be overlapping;
(4) battery that finishes of ordering directly enters the disinfection by ultraviolet light line, is dual-layer lamp tube up and down because battery disinfection by ultraviolet light line adopts, so guaranteed the pasteurised completely of battery, disinfecting time is controlled at 0.2m/min by the transfer rate of regulating netted conveyer belt;
(5) behind the disinfection by ultraviolet light, battery is directly delivered to disassemble on the platform to be disassembled, and mainly is wiring board and the plastic bottom cover of removing battery, thereby makes battery expose the discharge that both positive and negative polarity is convenient to battery; Battery after disassembling is placed in the conductive discharge case and discharges, and battery can be finished discharge about 3 hours;
(6) both sides and the bottom shell to battery positions cutting on the cutting machine of ventilator cowling being equipped with, ventilator cowling is connected on the air pipe, to discharge the volatility organic electrolyte that evaporates in the battery case cutting process, air pipe leads to the charcoal absorption case and absorbs the volatility organic electrolyte;
(7) will cut and carry out craft on the operating desk of battery in ventilator cowling of shell and disassemble, and collect respectively and comprise assemblies such as metal shell, aluminium foil, Copper Foil;
(8) with distilled water be medium, collected Copper Foil handled, to peel off the different electrode active materials that apply on aluminium foil and the Copper Foil by the ultrasonic wave that supersonic generator (1800W, side position ultrasonic head) produces; Electrode active material on the aluminium foil adopts N-methyl pyrrolidone solvent soaking to separate, and collects respectively.Peel off aluminium foil and the Copper Foil behind the electrode active material and cleaned with distilled water again, can directly obtain pure aluminium foil and Copper Foil.Handle metal shell with method, can obtain metal shell and plastics class material;
(9) the positive and negative electrode active material that strips down is the toner powder darkly, and major part is deposited in the bottom of generator, and collect the back respectively and use the distilled water rinsing clean, centrifugation, oven dry is sent to the hydrometallurgical recovery operation and is reclaimed metallic cobalt and lithium respectively.
Claims (13)
1. mobile phone lithium ion battery its recovery method as resource, the method includes the steps of: 1) battery sterilization; 2) battery ordering arrangement; 3) the surplus discharge of electricity of battery; 4) battery case cutting; 5) battery is disassembled with assembly and is sorted; 6) electrode active material is peeled off; 7) absorption of organic electrolyte.
2. mobile phone lithium ion battery its recovery method as resource as claimed in claim 1 is characterized in that: step 1) adopts the ozonization case of gas forced circulation convection current that waste mobile phone is sterilized, sterilized with lithium ion battery.
3. mobile phone lithium ion battery its recovery method as resource as claimed in claim 1 is characterized in that: in step 2) battery ordering arrangement before the size specification of battery is classified, and choose the bulge battery.
4. mobile phone lithium ion battery its recovery method as resource as claimed in claim 1 is characterized in that: step 3) is battery to be put into the conductive discharge case discharge residual electric energy.
5. mobile phone lithium ion battery its recovery method as resource as claimed in claim 4 is characterized in that: wiring board and the plastic bottom cover of removing battery before battery is put into the conductive discharge case.
6. mobile phone lithium ion battery its recovery method as resource as claimed in claim 1 is characterized in that: step 5) is disassembled the back to battery and is collected metal shell, aluminium foil, Copper Foil and plastic film.
7. mobile phone lithium ion battery its recovery method as resource as claimed in claim 1 is characterized in that: step 6) is carried out electrode material to the collected Copper Foil of step 5) by ultrasonic wave and is peeled off; Adopt appropriate organic solvent to soak to collected aluminium foil, to separate the electrode active material that applies on the aluminium foil.
8. mobile phone lithium ion battery its recovery method as resource as claimed in claim 7 is characterized in that: said organic solvent is the N-methyl pyrrolidone.
9. mobile phone lithium ion battery its recovery method as resource as claimed in claim 7 is characterized in that: supersonic generator is the supersonic generator of 1800W, side position ultrasonic head.
10. mobile phone lithium ion battery its recovery method as resource as claimed in claim 7 is characterized in that: the positive and negative electrode active material that strips down is collected afterwash, separation, oven dry, reclaims metallic cobalt and lithium respectively by Wet-process metallurgy method at last.
11. mobile phone as claimed in claim 1 lithium ion battery its recovery method as resource is characterized in that: step 7) is by exhaust duct the organic electrolyte volatilization gas to be entered the active carbon respiratory box to absorb, and purified gas is discharged.
12. mobile phone as claimed in claim 1 lithium ion battery its recovery method as resource is characterized in that: before step 3) battery is carried out disinfection by ultraviolet light.
13. mobile phone as claimed in claim 12 lithium ion battery its recovery method as resource is characterized in that: quartz burner has two-layer up and down, and battery is 0.1-0.5m/min by ultraviolet speed.
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CN102496752A (en) * | 2011-12-19 | 2012-06-13 | 中国海洋石油总公司 | Method for recycling electrolyte of waste lithium ion battery |
CN104143667A (en) * | 2013-08-23 | 2014-11-12 | 中航锂电(洛阳)有限公司 | Method and device for collection of waste lithium ion battery electrolyte solution |
CN105390764A (en) * | 2015-11-24 | 2016-03-09 | 国联汽车动力电池研究院有限责任公司 | High-pressure liquid cutting system and application thereof as well as dismantling method for waste lithium ion battery |
CN105417770A (en) * | 2015-11-13 | 2016-03-23 | 南通新宙邦电子材料有限公司 | Treatment method of waste liquor containing lithium hexafluorophosphate |
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