CN104183887A - Green method for dismantling, separation and recovery of waste LiCoO2 battery - Google Patents
Green method for dismantling, separation and recovery of waste LiCoO2 battery Download PDFInfo
- Publication number
- CN104183887A CN104183887A CN201410460074.3A CN201410460074A CN104183887A CN 104183887 A CN104183887 A CN 104183887A CN 201410460074 A CN201410460074 A CN 201410460074A CN 104183887 A CN104183887 A CN 104183887A
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- Prior art keywords
- positive electrode
- battery
- waste
- powder
- positive
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a green method for dismantling, separation and recovery of a waste LiCoO2 battery. The method comprises the following steps: (1) discharging a waste battery; (2) separating an electrolytic solution, collecting, and recovering a positive electrode sheet, a negative electrode sheet, a diaphragm and a shell; (3) mechanically grinding the positive electrode sheet and the negative electrode sheet respectively, and soaking the ground sheets in water or calcining the ground sheets to recover an aluminum foil and coarse positive electrode powder a of a positive electrode material, an aluminum foil and coarse positive electrode powder b; (4) mixing the coarse positive electrode powder a and the coarse positive electrode powder b, ball-mixing, sieving, and calcining in a muffle furnace to obtain fine positive electrode powder; and (5) modifying the fine positive electrode powder. The green method disclosed by the invention has the beneficial effects of being capable of achieving the green dismantling, separation and recovery of the waste lithium ion battery and is free from secondary pollution; after recovered LiCoO2 is modified, an industrial requirement is met; valuable materials such as the aluminum foil, a copper film and tags are recovered and separated, so as to effectively solve problems of harm of the lithium ion battery on environment and resource shortage.
Description
Technical field
The invention belongs to the treatment technology of recycling used batteries, particularly a kind of waste and old LiCoO
2battery green is disassembled separation and recovery method.
Background technology
Along with the consumption of China's lithium ion battery sharply increases, will be faced with a large amount of old and useless batterys future and need problem to be processed, bad if these old and useless batterys are not processed or processed, not only pollute the environment, but also can cause the wasting of resources.
Although the existing waste and old lithium ion battery recovery technology of China is more at present, these equipment and technique are only applicable to the digital lithium ion battery LiCoO that contains the rare precious metals such as Co
2type (ternary form), first by acid-soluble positive electrode formation Co
2+, Li
+deng, then reclaim CoSO by extraction, chemical precipitation method or electrolysis
4, Li
2cO
3, CoC
2o
4, Co (OH)
2, metal Co etc.But these methods are used a large amount of organic reagents to comprise acid, extractant, can cause secondary pollution to environment; Complex process, to equipment require high; Added value is low, and cost is high.Make for above-mentioned reasons LiCoO
2the recovery of battery is unsatisfactory, the invention enables LiCoO
2the recovery of battery green high-efficient more, the material after modification meets the requirement of technical grade, has realized recycling of material.
Summary of the invention
The object of the invention is to for above-mentioned existing problems, a kind of waste and old LiCoO is provided
2battery green is disassembled separation and recovery method, the requirement that with respect to prior art, the method technique is simple, efficiency is high, cost is low, recovery is comprehensive, electrode material after environmental protection, modification meets technical grade.
A kind of waste and old LiCoO
2battery green is disassembled separation and recovery method, comprises the following steps:
1) old and useless battery is put into the bucket stirring that fills water and metal powder, to waste and old LiCoO
2battery carries out short circuit dischange processing;
2) in stuffing box, battery after electric discharge is taken apart, put into centrifugal barrel and throw away electrolyte and collect, artificial separation obtains positive plate, negative plate, barrier film, shell and cleans respectively, positive plate after cleaning, negative plate, barrier film, shell are transferred to case dries outward, in case, after gas purification, discharges;
3) respectively by positive plate and negative plate mechanical crushing, the negative plate of pulverizing is immersed in deionized water and stirring, cleaning, filtration, oven dry, obtains respectively negative material and clean copper foil; Positive plate after pulverizing in Muffle furnace 350-450 DEG C of calcining 1-2h with except no-bonder, then cross 50 mesh standard sieves, obtain the aluminium foil that contains a small amount of positive electrode, the positive very coarse powder material a that contains a small amount of aluminium bits, the aluminium foil that contains a small amount of positive electrode is cleaned, filters, dried, the positive very coarse powder material b that obtains clean aluminium foil and contain a small amount of aluminium bits;
4) positive very coarse powder material a, the b that two parts obtained above is contained to a small amount of aluminium bits is mixed and carries out ball milling, crosses 400 mesh standard sieves to remove the aluminium bits that contain, residue powder 650-800 DEG C of calcining 2-3h in Muffle furnace, to remove conductive agent, obtained to positive electrode fine powder material;
5) above-mentioned positive electrode fine powder material is measured to the content of Li and Co by ICP, added lithium carbonate 800-950 DEG C of calcining 12h in Muffle furnace in the ratio of the mol ratio of Li and Co 1.05, ball milling is crossed 400 mesh standard sieves, obtains the LiCoO of modification
2.
Described metal powder is iron powder, zinc powder, aluminium powder or copper powder.
Described step 1), 2) all carry out being sealed in casing, operating personnel by gloves at case manipulation in vitro, waste gas in casing guides successively by entering atmosphere after 1-METHYLPYRROLIDONE (NMP) waste liquid, sig water, three grades of purified treatment of water by pipeline again, and saturated NMP waste liquid, sig water, water all enter the NMP recycled in its entirety system of battery enterprise.
The beneficial effect of the inventive method is: the method has realized the green of waste and old lithium ion battery and disassembled separation recovery, does not produce secondary pollution; To the LiCoO reclaiming
2realize effective modification, the LiCoO of modification
2positive electrode meets the requirement of technical grade; Aluminium foil, Copper Foil, lug etc. have valency material also to realize to reclaim and separate, the effective harm of lithium ion battery to environment and shortage problem of resource of having solved.
Brief description of the drawings
Fig. 1 is process flow diagram of the present invention.
Fig. 2 is the LiCoO of 900 DEG C of 12h modifications
2xRD.
Fig. 3 is the LiCoO of 900 DEG C of 12h modifications
2cycle performance curve.
Fig. 4 is the LiCoO of 950 DEG C of 12h modifications
2xRD.
Fig. 5 is the LiCoO of 950 DEG C of 12h modifications
2cycle performance curve.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing, the present invention is further elaborated.
Embodiment 1:
A kind of waste and old LiCoO
2battery green is disassembled separation and recovery method, as shown in Figure 1, comprises the following steps:
1) old and useless battery is put into the bucket stirring that fills water and iron powder, to waste and old LiCoO
2battery carries out short circuit dischange processing;
2) in stuffing box, battery after electric discharge is taken apart, put into centrifugal barrel and throw away electrolyte and collect, artificial separation obtains positive plate, negative plate, barrier film, shell and cleans respectively, positive plate after cleaning, negative plate, barrier film, shell are transferred to case dries outward, in case, after gas purification, discharges;
Described step 1), 2) all carry out being sealed in casing, operating personnel by gloves at case manipulation in vitro, waste gas in casing guides successively by entering atmosphere after 1-METHYLPYRROLIDONE (NMP) waste liquid, sig water, three grades of purified treatment of water by pipeline again, and saturated NMP waste liquid, sig water, water all enter the NMP recycled in its entirety system of battery enterprise;
3) respectively by positive plate and negative plate mechanical crushing, the negative plate of pulverizing is immersed in deionized water and stirring, cleaning, filtration, oven dry, obtains respectively negative material and clean copper foil; Positive plate after pulverizing in Muffle furnace 450 DEG C of calcining 1h with except no-bonder, then cross 50 mesh standard sieves, obtain the aluminium foil that contains a small amount of positive electrode, the positive very coarse powder material a that contains a small amount of aluminium bits, the aluminium foil that contains a small amount of positive electrode is cleaned, filters, dried, the positive very coarse powder material b that obtains clean aluminium foil and contain a small amount of aluminium bits;
4) positive very coarse powder material a, the b that two parts obtained above is contained to a small amount of aluminium bits is mixed and carries out ball milling, crosses 400 mesh standard sieves to remove the aluminium bits that contain, residue powder 650 DEG C of calcining 3h in Muffle furnace, to remove conductive agent, are obtained to positive electrode fine powder material;
5) above-mentioned positive electrode fine powder material is measured to the content of Li and Co by ICP, added lithium carbonate 900 DEG C of calcining 12h in Muffle furnace in the ratio of the mol ratio of Li and Co 1.05, ball milling is crossed 400 mesh standard sieves, obtains the LiCoO of modification
2.
The LiCoO of modification
2positive electrode has good layer structure, as shown in Figure 2; LiCoO after modification
2discharge capacity at 0.2C can reach 152 mAh/g, and has good cycle performance, as shown in Figure 3.LiCoO after modification
2tap density, average grain diameter (D50), pH value be respectively 2.366 g ml
-1, 12.49 um, 8.89, all meet the requirement of technical grade.
Embodiment 2:
A kind of waste and old LiCoO
2battery green is disassembled separation and recovery method, as shown in Figure 1, comprises the following steps:
1) old and useless battery is put into the bucket stirring that fills water and zinc powder, to waste and old LiCoO
2battery carries out short circuit dischange processing;
2) in stuffing box, battery after electric discharge is taken apart, put into centrifugal barrel and throw away electrolyte and collect, artificial separation obtains positive plate, negative plate, barrier film, shell and cleans respectively, positive plate after cleaning, negative plate, barrier film, shell are transferred to case dries outward, in case, after gas purification, discharges;
Described step 1), 2) all carry out being sealed in casing, operating personnel by gloves at case manipulation in vitro, waste gas in casing guides successively by entering atmosphere after 1-METHYLPYRROLIDONE (NMP) waste liquid, sig water, three grades of purified treatment of water by pipeline again, and saturated NMP waste liquid, sig water, water all enter the NMP recycled in its entirety system of battery enterprise;
3) respectively by positive plate and negative plate mechanical crushing, the negative plate of pulverizing is immersed in deionized water and stirring, cleaning, filtration, oven dry, obtains respectively negative material and clean copper foil; Positive plate after pulverizing in Muffle furnace 350 DEG C of calcining 2h with except no-bonder, then cross 50 mesh standard sieves, obtain the aluminium foil that contains a small amount of positive electrode, the positive very coarse powder material a that contains a small amount of aluminium bits, the aluminium foil that contains a small amount of positive electrode is cleaned, filters, dried, the positive very coarse powder material b that obtains clean aluminium foil and contain a small amount of aluminium bits;
4) positive very coarse powder material a, the b that two parts obtained above is contained to a small amount of aluminium bits is mixed and carries out ball milling, crosses 400 mesh standard sieves to remove the aluminium bits that contain, residue powder 800 DEG C of calcining 2h in Muffle furnace, to remove conductive agent, are obtained to positive electrode fine powder material;
5) above-mentioned positive electrode fine powder material is measured to the content of Li and Co by ICP, added lithium carbonate 950 DEG C of calcining 12h in Muffle furnace in the ratio of the mol ratio of Li and Co 1.05, ball milling is crossed 400 mesh standard sieves, obtains the LiCoO of modification
2.
The LiCoO of modification
2there is good layer structure, as shown in Figure 4; LiCoO after modification
2discharge capacity at 0.2C can reach 150 mAh/g, and has good cycle performance, as shown in Figure 5.LiCoO after modification
2tap density, average grain diameter (D50), pH value be respectively 2.228 g ml
-1, 19.71 um, 8.65, all meet the requirement of technical grade.
Claims (3)
1. a waste and old LiCoO
2battery green is disassembled separation and recovery method, it is characterized in that comprising the following steps:
1) old and useless battery is put into the bucket stirring that fills water and metal powder, to waste and old LiCoO
2battery carries out short circuit dischange processing;
2) in stuffing box, battery after electric discharge is taken apart, put into centrifugal barrel and throw away electrolyte and collect, artificial separation obtains positive plate, negative plate, barrier film, shell and cleans respectively, positive plate after cleaning, negative plate, barrier film, shell are transferred to case dries outward, in case, after gas purification, discharges;
3) respectively by positive plate and negative plate mechanical crushing, the negative plate of pulverizing is immersed in deionized water and stirring, cleaning, filtration, oven dry, obtains respectively negative material and clean copper foil; Positive plate after pulverizing in Muffle furnace 350-450 DEG C of calcining 1-2h with except no-bonder, then cross 50 mesh standard sieves, obtain the aluminium foil that contains a small amount of positive electrode, the positive very coarse powder material a that contains a small amount of aluminium bits, the aluminium foil that contains a small amount of positive electrode is cleaned, filters, dried, the positive very coarse powder material b that obtains clean aluminium foil and contain a small amount of aluminium bits;
4) positive very coarse powder material a, the b that two parts obtained above is contained to a small amount of aluminium bits is mixed and carries out ball milling, crosses 400 mesh standard sieves to remove the aluminium bits that contain, residue powder 650-800 DEG C of calcining 2-3h in Muffle furnace, to remove conductive agent, obtained to positive electrode fine powder material;
5) above-mentioned positive electrode fine powder material is measured to the content of Li and Co by ICP, added lithium carbonate 800-950 DEG C of calcining 12h in Muffle furnace in the ratio of the mol ratio of Li and Co 1.05, ball milling is crossed 400 mesh standard sieves, obtains the LiCoO of modification
2.
2. waste and old LiCoO according to claim 1
2battery green is disassembled separation and recovery method, it is characterized in that: described metal powder is iron powder, zinc powder, aluminium powder or copper powder.
3. waste and old LiCoO according to claim 1
2battery green is disassembled separation and recovery method, it is characterized in that: described step 1), 2) all carry out being sealed in casing, operating personnel by gloves at case manipulation in vitro, waste gas in casing guides successively by entering atmosphere after 1-METHYLPYRROLIDONE (NMP) waste liquid, sig water, three grades of purified treatment of water by pipeline again, and saturated NMP waste liquid, sig water, water all enter the NMP recycled in its entirety system of battery enterprise.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410460074.3A CN104183887A (en) | 2014-09-11 | 2014-09-11 | Green method for dismantling, separation and recovery of waste LiCoO2 battery |
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|---|---|---|---|
| CN201410460074.3A CN104183887A (en) | 2014-09-11 | 2014-09-11 | Green method for dismantling, separation and recovery of waste LiCoO2 battery |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104485493A (en) * | 2014-12-30 | 2015-04-01 | 兰州理工大学 | Repair and regeneration method for lithium cobaltate positive active material in waste lithium ion battery |
| CN105304971A (en) * | 2015-11-30 | 2016-02-03 | 中国科学院生态环境研究中心 | Mechanochemistry recycling method of waste lithium battery cathode material |
| CN105742743A (en) * | 2016-01-18 | 2016-07-06 | 江南石墨烯研究院 | Method for recycling separator material from waste lithium ion battery |
| CN105958150A (en) * | 2016-06-30 | 2016-09-21 | 普定县银丰农业科技发展有限公司 | Comprehensive utilization method for waste lithium ion batteries |
| CN106450557A (en) * | 2016-11-30 | 2017-02-22 | 荆门市格林美新材料有限公司 | Method for separating anode material and aluminum from anode plate of waste battery |
| CN111370794A (en) * | 2020-03-19 | 2020-07-03 | 河南小威环境科技有限公司 | Method for releasing electric quantity of lithium ion battery |
| CN113904020A (en) * | 2021-11-10 | 2022-01-07 | 苏州博萃循环科技有限公司 | Cyclic regeneration method of waste lithium ion battery active material and lithium ion battery active material |
| CN114426312A (en) * | 2022-01-13 | 2022-05-03 | 南京同宁新材料研究院有限公司 | Method for preparing high-pressure lithium cobaltate by using waste lithium cobaltate |
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| CN1953269A (en) * | 2006-11-01 | 2007-04-25 | 浙江工业大学 | A recovery method for waste lithium ion cell |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104485493A (en) * | 2014-12-30 | 2015-04-01 | 兰州理工大学 | Repair and regeneration method for lithium cobaltate positive active material in waste lithium ion battery |
| CN105304971A (en) * | 2015-11-30 | 2016-02-03 | 中国科学院生态环境研究中心 | Mechanochemistry recycling method of waste lithium battery cathode material |
| CN105304971B (en) * | 2015-11-30 | 2019-03-15 | 中国科学院生态环境研究中心 | The mechanochemistry recoverying and utilizing method of waste lithium cell positive electrode |
| CN105742743A (en) * | 2016-01-18 | 2016-07-06 | 江南石墨烯研究院 | Method for recycling separator material from waste lithium ion battery |
| CN105958150A (en) * | 2016-06-30 | 2016-09-21 | 普定县银丰农业科技发展有限公司 | Comprehensive utilization method for waste lithium ion batteries |
| CN105958150B (en) * | 2016-06-30 | 2019-07-12 | 普定县银丰农业科技发展有限公司 | A kind of method of comprehensive utilization of waste and old lithium ion battery |
| CN106450557A (en) * | 2016-11-30 | 2017-02-22 | 荆门市格林美新材料有限公司 | Method for separating anode material and aluminum from anode plate of waste battery |
| CN106450557B (en) * | 2016-11-30 | 2019-06-11 | 荆门市格林美新材料有限公司 | The method of the positive electrode and aluminium of separating waste, worn anode on piece |
| CN111370794A (en) * | 2020-03-19 | 2020-07-03 | 河南小威环境科技有限公司 | Method for releasing electric quantity of lithium ion battery |
| CN113904020A (en) * | 2021-11-10 | 2022-01-07 | 苏州博萃循环科技有限公司 | Cyclic regeneration method of waste lithium ion battery active material and lithium ion battery active material |
| CN114426312A (en) * | 2022-01-13 | 2022-05-03 | 南京同宁新材料研究院有限公司 | Method for preparing high-pressure lithium cobaltate by using waste lithium cobaltate |
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Application publication date: 20141203 |