CN102412430B - Chemical separating method for aluminum foil in waste lithium ion battery positive plate - Google Patents
Chemical separating method for aluminum foil in waste lithium ion battery positive plate Download PDFInfo
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- CN102412430B CN102412430B CN201110357947.4A CN201110357947A CN102412430B CN 102412430 B CN102412430 B CN 102412430B CN 201110357947 A CN201110357947 A CN 201110357947A CN 102412430 B CN102412430 B CN 102412430B
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- 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 chemical separating method for an aluminum foil in a waste lithium ion battery positive plate. The method comprises the following steps of: (1) adding the waste lithium ion battery positive plate into a surfactant solution, performing ultrasonic oscillation treatment to loosen surface components of the positive plate, washing, drying, filtering and recovering the positive plate; (2) putting the positive plate treated in the step (1) into a mixed solution of N, N-dimethylacetamide and N-methylpyrrolidone, heating, taking the positive plate out, and washing with water; (3) putting positive plate treated in the step (2) into water, performing ultrasonic oscillation till the aluminum foil as well as active substances of an anode, a conducting agent and a bonding agent; and (4) filtering a solution obtained in step (3), washing to obtain a mixture containing the active substances, the conducting agent, the bonding agent and the aluminum foil, and screening to obtain a dissociative aluminum foil sheet. In the method, the aluminum foil sheet can be recovered directly; and compared with the conventional method for extracting an aluminum foil after dissolving with alkali, the chemical separating method has the advantages: the process is simplified, and cost is lowered.
Description
Technical field
The present invention relates to a kind of separation method of aluminium foil of waste lithium ion cell anode sheet, relate in particular to the Chemical Decomposition method of aluminium foil in a kind of waste lithium ion cell anode sheet.
Background technology
Along with the sustainable growth of lithium battery consumption, the leftover bits that produce in lithium battery manufacturing process and relic are also more and more.A lot of lithium battery manufacturers and the processing of waste disposal unit to this class industrial waste, conventionally battery cut, pulverize, dry, acid is molten, separation obtains the metal or the compound that need.Although this processing method has been extracted the useful rare element of part, in leaching process, use other chemical substances with no options to destroy all the components, form the byproduct of Multiple components complexity, cannot meet recovery requirement efficient, Gao Xuan.
At present, recovery method is mainly the problem of peeling off that is manually split as the positive and negative electrode collector of master, especially battery core, is subject to the effects such as binding agent, and adhesive force is very strong, and manual removal efficiency is very low, and related a large amount of positive electrodes and conductive agent on collector.At present, also have some methods about the separated aluminium foil of positive plate to mainly contain:
The people's such as Tang Village " high efficient stripping method of collective's fluid in waste lithium cell recovery " (CN 101217206A), proposition is by both positive and negative polarity together heat treatment, then vibrosieve, separating active substances and base material, use again alkali solution technique aluminium separated with alkaline precipitation and copper, finally with the form of aluminium hydroxide, extract aluminium.This method is processed both positive and negative polarity together, makes complicated component, has increased the step of separated aluminium and copper.
" a kind of comprehensive recovering process of positive pole waste tablet from ferric phosphate lithium cell " (CN 101383441A) of the people such as Zhou Dong; first broken anodal useless sheet is proposed; then under inert gas shielding, heat-treat; machinery separation obtains the mixture of active material, aluminium foil, conductive agent and binding agent again; finally control aperture and sieve, obtain aluminium foil.This method need to be used protective gas, and cost is higher, adds that the screening of multiple mixture is difficult to guarantee completely separated.
Summary of the invention
Object of the present invention provides the Chemical Decomposition method of aluminium foil in a kind of simple, waste lithium ion cell anode sheet that cost is low.
Goal of the invention of the present invention is achieved through the following technical solutions: a kind of Chemical Decomposition method of aluminium foil in waste lithium ion cell anode sheet, comprises the following steps:
(1) waste lithium ion cell anode sheet is added in surfactant solution, sonic oscillation is processed, and makes pole piece surface composition become loose, then cleans, dry, filtered and recycled pole piece;
(2) pole piece after step (1) is processed is put into the mixed solution of DMA and 1-METHYLPYRROLIDONE, carried out heat treated, then take out, water cleans;
(3) pole piece after step (2) is processed is placed in to water, sonic oscillation to aluminium foil and anodal active material, conductive agent and binding agent peeled off;
(4) solution of step (3) gained after filtration, cleans, and obtains the mixture containing active material, conductive agent, binding agent and aluminium foil, through screening, obtains free aluminium foil.
In the surfactant solution of step of the present invention (1), the concentration of contained surfactant is 0.5 ~ 1g/L.Described surfactant is at least one in neopelex, sodium lauryl tri(oxyethyl) sulfate, NPE, sapn, tween and stearic acid.And when in surfactant solution, contained surfactant is two or more, the concentration of every kind of surfactant is all 0.5 ~ 1g/L.
The time of the sonic oscillation in described step (1) is 10 ~ 20 min.
Pole piece in described step (1) and the mass volume ratio of surfactant solution are 5-10g/L.
In the DMA of step of the present invention (2) and the mixed solution of 1-METHYLPYRROLIDONE, the volume ratio of DMA solution and 1-METHYLPYRROLIDONE solution is 1:2.5 ~ 1:3; The mass volume ratio of the mixed solution of described pole piece and DMA and 1-METHYLPYRROLIDONE is 5 ~ 10 g/L.
The temperature of the heat treated of described step (2) is between 60 ~ 90 ℃ of scopes, and constant temperature is processed 1 ~ 2 h.
The time that the sonic oscillation of step of the present invention (3) is processed is between 10 ~ 20s scope.
The waste lithium ion cell anode sheet of step of the present invention (1) first cuts into small pieces before carrying out separating treatment, facilitates separated operation and screening.
The present invention can directly take out separated with anodal active material, conductive agent and binding agent aluminium foil in described step (2), or is left to next step and sieves;
compared with prior art, the present invention has following beneficial effect:
(1) fine and close due to pole piece surface composition, organic solvent is not good to binding agent solute effect, thus the present invention before dissolving binding agent to pole piece sonic oscillation, make surface composition loose, strengthen solute effect.
(2) pin the present invention adopts organic solvent N, N-dimethylacetylamide and 1-METHYLPYRROLIDONE mixed solution dissolve, the mixing match of the lytic agent in this mixed solution is suitable, has solved the single lytic agent problem bad to conventional binding agent solute effect.
(3) the present invention processes full wafer pole piece or the pole piece that cuts into certain size size, need not carry out break process to pole piece, not only convenient screening, can also in processing procedure, directly reclaim aluminium foil, with respect to the molten aluminium foil of traditional alkali, extract again the method for aluminium, more simplified operation, reduced cost.
Embodiment
embodiment 1:
(1) waste lithium ion cell anode sheet is cut into small pieces, approximately 5 cm * 5 cm;
(2) 0.5 g pole piece being added to 100mL concentration is in the neopelex solution of 0.5 g/L, and sonic oscillation 10min takes out, and cleans, and makes pole piece surface composition become loose, filtered and recycled pole piece.
(3) N, N-dimethylacetamide solution and 1-METHYLPYRROLIDONE solution by volume 1:2.5 are mixed into mixed solution, pole piece is placed in to reactive tank, add 100mL N, the mixed solution of N-dimethylacetylamide and 1-METHYLPYRROLIDONE, is heated to 60 ℃, constant temperature 2 h, take out, water cleans;
(4) pole piece is placed in to water, sonic oscillation 10s, aluminium foil and anodal active material, conductive agent and binding agent are peeled off, and separated with anodal active material, conductive agent and binding agent aluminium foil directly can be taken out, or be left to next step and sieve in this step;
(5) solution filter of step (4), cleans pole piece, obtains the mixture containing active material, conductive agent, binding agent and aluminium foil fragment, through screening, obtains free aluminium foil fragment.
embodiment 2:
(1) waste lithium ion cell anode sheet is cut into small pieces, approximately 5 cm * 5 cm;
(2) 1 g pole piece being added to 100mL concentration is in the sodium lauryl tri(oxyethyl) sulfate solution of 1 g/L, and sonic oscillation 20min takes out, and cleans, and makes pole piece surface composition become loose, filtered and recycled pole piece.
(3) N, N-dimethylacetamide solution and 1-METHYLPYRROLIDONE solution by volume 1:3 are mixed into mixed solution, pole piece is placed in to reactive tank, add 100mL N, the mixed solution of N-dimethylacetylamide and 1-METHYLPYRROLIDONE, is heated to 80 ℃, constant temperature 1 h, take out, water cleans;
(4) pole piece is placed in to water, sonic oscillation 20s, aluminium foil and anodal active material, conductive agent and binding agent are peeled off, and separated with anodal active material, conductive agent and binding agent aluminium foil directly can be taken out, or be left to next step and sieve in this step;
(5) solution filter of step (4), cleans pole piece, obtains the mixture containing active material, conductive agent, binding agent and aluminium foil fragment, through screening, obtains free aluminium foil fragment.
embodiment 3:
(1) waste lithium ion cell anode sheet is cut into small pieces, approximately 5 cm * 5 cm;
(2) 0.8 g pole piece being added to 100mL concentration is in the NPE solution of 0.8 g/L, and sonic oscillation 15min takes out, and cleans, and makes pole piece surface composition become loose, filtered and recycled pole piece.
(3) N, N-dimethylacetamide solution and 1-METHYLPYRROLIDONE solution by volume 1:2.6 are mixed into mixed solution, pole piece is placed in to reactive tank, add 100mL N, the mixed solution of N-dimethylacetylamide and 1-METHYLPYRROLIDONE, is heated to 70 ℃, constant temperature 2 h, take out, water cleans;
(4) pole piece is placed in to water, sonic oscillation 15s, aluminium foil and anodal active material, conductive agent and binding agent are peeled off, and separated with anodal active material, conductive agent and binding agent aluminium foil directly can be taken out, or be left to next step and sieve in this step;
(5) solution filter of step (4), cleans pole piece, obtains the mixture containing active material, conductive agent, binding agent and aluminium foil fragment, through screening, obtains free aluminium foil fragment.
embodiment 4:
(1) waste lithium ion cell anode sheet is cut into small pieces, approximately 5 cm * 5 cm;
(2) 0.9g pole piece being added to 100mL concentration is in the mixed solution of the neopelex of 0.5 g/L and the sodium lauryl tri(oxyethyl) sulfate solution of 0.5 g/L, sonic oscillation 15min, takes out, and cleans, make pole piece surface composition become loose, filtered and recycled pole piece.
(3) N, N-dimethylacetamide solution and 1-METHYLPYRROLIDONE solution by volume 1:2.8 are mixed into mixed solution, pole piece is placed in to reactive tank, adding 100mL volume ratio is the N of 1:2.8, the mixed solution of N-dimethylacetylamide and 1-METHYLPYRROLIDONE, is heated to 80 ℃, constant temperature 1.5 h, take out, water cleans;
(4) pole piece is placed in to water, sonic oscillation 15s, aluminium foil and anodal active material, conductive agent and binding agent are peeled off, and separated with anodal active material, conductive agent and binding agent aluminium foil directly can be taken out, or be left to next step and sieve in this step;
(5) solution filter of step (4), cleans pole piece, obtains the mixture containing active material, conductive agent, binding agent and aluminium foil fragment, through screening, obtains free aluminium foil fragment.
The present invention can summarize with other the concrete form without prejudice to spirit of the present invention or principal character.Above-mentioned embodiment of the present invention all can only be thought explanation of the present invention rather than restriction, therefore every foundation essence technology of the present invention is done above embodiment any trickle modification, equivalent variations and modification, all belong in the scope of technical solution of the present invention.
Claims (6)
1. a Chemical Decomposition method for the aluminium foil of waste lithium ion cell anode sheet, is characterized in that, comprises the following steps:
(1) waste lithium ion cell anode sheet is cut into small pieces, by mass volume ratio 5 ~ 10g/L, add in surfactant solution, sonic oscillation is processed, and makes pole piece surface composition become loose, then cleans, dry, filtered and recycled pole piece;
(2) pole piece after step (1) is processed is put into the mixed solution of DMA and 1-METHYLPYRROLIDONE by mass volume ratio 5 ~ 10 g/L, carry out heat treated, then take out, water cleans; In the mixed solution of described DMA and 1-METHYLPYRROLIDONE, the volume ratio of DMA solution and 1-METHYLPYRROLIDONE solution is 1:2.5 ~ 1:3; (3) pole piece after step (2) is processed is placed in to water, sonic oscillation to aluminium foil and anodal active material, conductive agent and binding agent peeled off;
(4) solution of step (3) after filtration, cleans, and obtains the mixture containing active material, conductive agent, binding agent and aluminium foil, through screening, obtains free aluminium foil.
2. the Chemical Decomposition method of the aluminium foil of waste lithium ion cell anode sheet according to claim 1, is characterized in that, in the surfactant solution of described step (1), the concentration of contained surfactant is 0.5 ~ 1g/L.
3. the Chemical Decomposition method of the aluminium foil of waste lithium ion cell anode sheet according to claim 1 and 2, is characterized in that, the time of the sonic oscillation in described step (1) is 10 ~ 20 min.
4. the Chemical Decomposition method of the aluminium foil of waste lithium ion cell anode sheet according to claim 3, is characterized in that, the temperature of the heat treated of described step (2) is between 60 ~ 90 ℃ of scopes, and constant temperature is processed 1 ~ 2 h.
5. the Chemical Decomposition method of the aluminium foil of waste lithium ion cell anode sheet according to claim 4, is characterized in that, the time that the sonic oscillation of described step (3) is processed is between 10 ~ 20 s scopes.
6. the Chemical Decomposition method of the aluminium foil of waste lithium ion cell anode sheet according to claim 4, it is characterized in that, described surfactant is at least one in neopelex, sodium lauryl tri(oxyethyl) sulfate, NPE, sapn, tween and stearic acid.
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| CN201110357947.4A CN102412430B (en) | 2011-11-14 | 2011-11-14 | Chemical separating method for aluminum foil in waste lithium ion battery positive plate |
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| CN201110357947.4A CN102412430B (en) | 2011-11-14 | 2011-11-14 | Chemical separating method for aluminum foil in waste lithium ion battery positive plate |
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| JP5464137B2 (en) * | 2010-12-14 | 2014-04-09 | 住友金属鉱山株式会社 | Method for separating positive electrode active material and method for recovering valuable metal from lithium ion battery |
| CN103066343B (en) * | 2012-12-21 | 2015-03-11 | 中南大学 | Method for processing separated active matter and aluminum in lithium ion battery positive plate |
| CN105355997B (en) * | 2015-10-16 | 2018-04-17 | 李佳坤 | A kind of separation method and its application of lithium battery collector and active material |
| CN105244564B (en) * | 2015-11-14 | 2017-07-04 | 福州大学 | A kind of recoverying and utilizing method of lithium iron phosphate dynamic battery |
| CN105356000A (en) * | 2015-12-10 | 2016-02-24 | 华南师范大学 | Recovering method of LiFePO4 positive electrode in spent lithium-ion battery |
| CN105428747A (en) * | 2015-12-30 | 2016-03-23 | 深圳先进技术研究院 | Restoration and recycling method of lithium cobaltate materials of lithium batteries |
| CN106684485B (en) * | 2016-12-19 | 2020-04-21 | 天齐锂业股份有限公司 | Method for recycling waste lithium iron phosphate anode material by acid leaching method |
| CN107785632B (en) * | 2017-09-28 | 2019-08-27 | 湖北大学 | A kind of stripping means of cylinder-shaped lithium ion battery air-stable positive electrode active materials |
| CN108336440B (en) * | 2018-01-05 | 2020-04-07 | 深圳市比克电池有限公司 | Method for recovering waste lithium ion battery current collector |
| CN111261969B (en) * | 2020-02-05 | 2021-08-17 | 中国科学院化学研究所 | Method for recycling and regenerating lithium iron phosphate waste battery anode material |
| CN112164834B (en) * | 2020-09-30 | 2022-05-24 | 武汉大学 | Regeneration method of waste lithium iron phosphate battery positive electrode material |
| CN112467241B (en) * | 2020-11-12 | 2022-07-22 | 郑州中科新兴产业技术研究院 | Short-process recycling method for ternary cathode material, recycled material and application |
| CN113193255B (en) * | 2021-04-14 | 2022-10-04 | 成都工业职业技术学院 | New energy battery material recycling and regenerating treatment method |
| CN114204149B (en) * | 2021-11-24 | 2023-04-11 | 华中科技大学 | Method for separating electrode material from retired lithium battery pole piece and application thereof |
| CN113909273B (en) * | 2021-12-07 | 2022-06-28 | 中国科学院过程工程研究所 | Waste lithium battery pole piece recycling method and application |
| CN114639887A (en) * | 2022-03-15 | 2022-06-17 | 金川集团股份有限公司 | Method for separating anode powder and current collector in lithium ion battery pole piece |
| CN115896455B (en) * | 2022-10-28 | 2024-03-08 | 广东邦普循环科技有限公司 | Recycling and processing equipment and method for waste lithium battery positive plate |
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| EP0842304B1 (en) * | 1995-07-26 | 1999-04-21 | Societe Nouvelle d'Affinage des Metaux SNAM | Method for processing scrap containing one or more alloys that react to form hydrides, to enable recycling thereof |
| CN1747224A (en) * | 2005-09-13 | 2006-03-15 | 天津大学 | Production of LixCoO2 from recovering waste lithium ionic battery |
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