CN105870529A - Recovery method for waste lithium ion batteries - Google Patents
Recovery method for waste lithium ion batteries Download PDFInfo
- Publication number
- CN105870529A CN105870529A CN201610284928.6A CN201610284928A CN105870529A CN 105870529 A CN105870529 A CN 105870529A CN 201610284928 A CN201610284928 A CN 201610284928A CN 105870529 A CN105870529 A CN 105870529A
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- CN
- China
- Prior art keywords
- positive
- negative
- lithium ion
- negative pole
- recovery method
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Classifications
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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 belongs to the field of lithium ion batteries, and provides a recovery method for waste lithium ion batteries. The method comprises the steps that the waste lithium ion batteries are placed in protective gas after being completely discharged to take out battery cells; the battery cells are placed in DMC and cleaned; positive and negative pole pieces in the battery cells are taken out, the positive pole pieces are arranged in NMP to be soaked and subjected to ultrasonic treatment, and positive pole current collectors and positive pole powder solutions are obtained; the negative pole pieces are placed in distilled water to be soaked and subjected to ultrasonic treatment, and negative pole current collectors and negative pole powder solutions are obtained; the positive and negative pole powder solutions are centrifuged, and positive and negative pole powder is collected and recycled after being dried. Te recovery method is short in time, high in operability and low in treating difficulty, can solve the disposition problem of lithium ion battery carbon negative poles, achieves comprehensive recovery of lithium ion battery positive and negative poles and is of positive significance in environmental protection.
Description
Technical field
The invention belongs to field of lithium ion battery, particularly relate to a kind of waste and old lithium ion battery recovery method.
Background technology
In existing battery applications field, lithium ion battery is with its high security, good hot properties, length
Cycle life, the highest attention that environmentally friendly, the advantage such as wide, cheap of originating causes people, and return
Receipts problem is again faced by lithium ion battery is had to after a procedure.Waste and old lithium ion battery resource is returned at present
Receive treatment research and focus primarily upon costly positive pole precious metal cobalt and the recycling of lithium, owing to lacking
Understanding to lithium ion batteries anodes waste paper recovery value, the negative pole waste paper after generally using is often
Directly discarded.
The recovery of the lithium electro-graphitic cathode pole piece reported uses the side such as high-temperature calcination, broken, soda acid immersion more
Method makes dressing peel off from collector, this recovery method exist energy consumption compared with high, separating difficulty is big, solvent is rotten
The problem that erosion intensity is big, be easily generated secondary pollution etc..Meanwhile, the electrolyte of lithium battery is for dissolving LiPF6(six
Lithium fluophosphate) etc. the organic solution of lithium salts, during simple high-temperature calcination, broken, soda acid immersion etc. easily
Causing the volatilization of electrolyte, will react after the moisture in electrolyte contacts water or air, generation has the strongest
The HF (hydrofluoric acid) of toxicity.Additionally, old and useless battery there may also be the Li dendrite of remnants, run in air
Moisture can heat even catch fire.
If be provided that a kind of method that waste and old lithium ion battery positive/negative plate is reclaimed comprehensively, it is possible not only to
Solve the problem existing for existing anode plate for lithium ionic cell recovery aspect, it is possible to realize lithium ion battery material
Comprehensive recovery of material.But, the most in the art, still lack such a environmental protection, strong operability,
And the method that negative electrode material of waste lithium ion battery is reclaimed comprehensively that intractability is low.
Summary of the invention
For solving above-mentioned technical problem, the invention provides a kind of waste and old lithium ion battery recovery method, it is intended to
Solve drawback present on existing lithium ion battery negative recovery method, it is achieved complete to waste and old lithium ion battery
Face is reclaimed.
The present invention is achieved in that a kind of waste and old lithium ion battery recovery method, comprises the following steps:
After waste and old lithium ion battery electric discharge completely, it is placed in protective gas taking-up battery core；
Gained battery core is placed in DMC (dimethyl carbonate) and soaks, clean；
Take out the positive and negative plate in battery core, positive plate is placed in NMP (1-METHYLPYRROLIDONE) soak,
Ultrasonically treated, it is thus achieved that plus plate current-collecting body and positive mix solution；Negative plate is placed in distilled water immersion, ultrasonic
Process, it is thus achieved that negative current collector and negative pole powder solution；
It is centrifuged positive and negative electrode powder solution respectively, collects positive and negative electrode powder, recycle after drying.
The present invention compared with prior art, has the beneficial effects that: lithium ion battery be have employed by patent of the present invention
It is processed by battery core immediately after shelling by the method for DMC leaching.The most both LiPF can have been eliminated6Hydrolysis
The hydrofluoric acid the generated impact on environment, it is possible to prevent the electrolyte volatilization impact on human and environment.Align,
Negative plate carries out process such as soaking, ultrasonic, makes positive and negative electrode powder peel off from collector efficiently, it is ensured that
The integrality of collector.
The present invention aligns according to the difference of both positive and negative polarity structure and composition, negative pole powder is separately recovered, timeliness
Short, strong operability, intractability are low, be possible not only to solve lithium ion batteries anodes handling problems, return
The carbon negative pole material received be usable in material with carbon element prepare, tire carbon dope, the aspect such as iron and steel steel-making, and to reality
Comprehensive recovery of the both positive and negative polarity of existing lithium battery, has positive meaning to environmental protection.
Accompanying drawing explanation
Fig. 1 is the waste and old lithium ion battery complete recovering technique flow chart that the present invention provides.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing and reality
Execute example, the present invention is further elaborated.Only should be appreciated that specific embodiment described herein
Only in order to explain the present invention, it is not intended to limit the present invention.
Technical scheme is as it is shown in figure 1, specifically include following steps:
Step one, after waste and old lithium ion battery electric discharge completely, is placed in protective gas taking-up battery core；
Step 2, is placed in DMC immersion by gained battery core, cleans；
Step 3, takes out the positive and negative plate in battery core, positive plate is placed in NMP heat, soak,
Ultrasonically treated, it is thus achieved that plus plate current-collecting body and positive mix solution；Negative plate be placed in distilled water heat, soak,
Ultrasonically treated, it is thus achieved that negative current collector and negative pole powder solution；Plus plate current-collecting body and negative current collector reclaim profit
With；
Step 4, is centrifuged positive and negative electrode powder solution respectively, collects positive and negative electrode powder, reclaims after drying.
Specifically, in step one, described protective gas is nitrogen or inert gas.
Specifically, in step 2, described soak time is 0.5-1h, is carried out with DMC, cleans secondary
Number is for 3-5 time.
Specifically, in step 3, described positive plate, the heating-up temperature of negative plate are 80-90 degree, ultrasonic place
The frequency of reason is 100-300W, and the time is 10-20min.
Specifically, in step 4, described centrifugal speed is 3000rpm, and the time is 5-10min.
The technical scheme is that after carried out waste and old lithium ion battery discharging, disassemble etc. processes,
Difference according to both positive and negative polarity structure and composition aligns, negative pole powder is separately recovered.
In the process of the present invention, it is contemplated that the electrolyte of lithium ion battery is for dissolving LiPF6Having Deng lithium salts
Machine solution, will react after the moisture in contact water or air, generate and have the most supervirulent HF (hydrofluoric acid).
Additionally, old and useless battery there may also be the Li dendrite of remnants, running into the moisture in air can heat even catch fire,
Therefore waste and old lithium ion battery be have employed to the battery core after shelling immediately with DMC leaching method at
Reason, the most both can eliminate LiPF6Hydrolyze the strong acid impact on environment of generation, prevent electrolyte from volatilizing to people
Impact with environment, it is also possible to realize the recycling of lithium salts.
Soak positive and negative plate, ultrasonic etc. processes, and binding agent decomposes and gradually loses cementation,
The dressing on pole piece is made naturally to peel off from collector fast and efficiently, as powder can not separate by sonic oscillation
Getting off, can heat immersion system, temperature is advisable less than 90 degree.Soak pole piece distilled water and
NMP, continues to recycle by the method for distillation after a procedure.Use this method process pole piece obtain just,
Negative current collector profile is complete, and is completely removed by the dusting on collector through ultrasonically treated, and surface is clean
Only, recycling is not affected.
The present invention, according to the difference of both positive and negative polarity structure and composition, aligns, negative pole powder reclaims respectively, protects
The integrality of card collector, and avoid collector to enter subsequent processing stage, eliminate the techniques such as the heavy aluminium of tradition
Step.This process simplify recovery process, shorten flow process, have that timeliness is short, strong operability, process difficult
Spend the advantages such as low, the most environmentally friendly.
The quality of final acquisition product is higher, and the positive mix of recovery can be used for preparing new lithium ion battery,
The negative pole powder reclaimed is prepared as carbon nanometer fragment, prepare for material with carbon element, tire carbon dope, iron and steel steel-making etc.
Aspect.Therefore the recovery method of the present invention achieves the money of component whole to positive and negative electrode in used Li ion cell
Sourceization reclaims, and has positive meaning to environmental protection.
Below in conjunction with specific embodiment, technical scheme is described in detail.
Embodiment 1
(1) collect waste lithium iron phosphate battery, first these cells are discharged completely；
(2) in the glove box of full inert gas, the single battery case solution discharged completely is cut open, takes
Go out battery core, be placed in DMC immersion 0.7h, then flush three times with DMC；
(3) waste lithium iron phosphate battery battery core removes glove box after DMC embathes, and takes out positive pole therein
Sheet and negative plate, positive plate is transferred in NMP, and cathode pole piece transfers to distilled water, shifts the most together
In supersonic cleaning machine, temperature furnishing 85 degree, with the hunting of frequency 10min of 200W；Collect acquisition respectively
Plus plate current-collecting body and positive mix solution, negative current collector and negative pole powder solution；
(4) the ultrasonic positive and negative electrode powder solution stripped down is respectively with distilled water repeatedly low-speed centrifugal
After (3000rpm, 5min) washing, collecting the powder obtained, in air dry oven, 100 DEG C are toasted and get final product
Just material is reclaimed to positive pole, negative pole.
(5) the negative pole carbon dust of recovery is processed further it is prepared as carbon nanometer fragment, prepare for material with carbon element,
Tire carbon dope or iron and steel steel-making；Positive mix will be lived again and be prepared positive electrode.
This method achieve waste lithium iron phosphate battery efficient, quickly separate and recover, simultaneously to environment friend
Good, it is achieved that in waste lithium iron phosphate battery, the resource of whole components reclaims.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all at this
Any amendment, equivalent and the improvement etc. made within bright spirit and principle, should be included in the present invention
Protection domain within.
Claims (7)
1. a waste and old lithium ion battery recovery method, it is characterised in that comprise the following steps:
After waste and old lithium ion battery electric discharge completely, it is placed in protective gas taking-up battery core；
Gained battery core is placed in DMC immersion, cleans；
Take out the positive and negative plate in battery core, positive plate be placed in NMP immersion, ultrasonically treated, it is thus achieved that
Plus plate current-collecting body and positive mix solution；Negative plate is placed in distilled water immersion, ultrasonically treated, it is thus achieved that negative pole
Collector and negative pole powder solution；
It is centrifuged positive and negative electrode powder solution respectively, collects positive and negative electrode powder, recycle after drying.
2. recovery method as claimed in claim 1, it is characterised in that described protective gas is nitrogen or lazy
Property gas.
3. recovery method as claimed in claim 1, it is characterised in that described battery core is placed in DMC leaching
The time of bubble is 0.5-1h.
4. recovery method as claimed in claim 1, it is characterised in that described positive plate, negative plate are carried out
Soak, ultrasonically treated time heat, the temperature of described heating is 80-90 degree.
5. recovery method as claimed in claim 1, it is characterised in that described positive plate, negative plate super
The frequency of sonication is 100-300W, and the time is 10-20min.
6. recovery method as claimed in claim 1, it is characterised in that described centrifugal speed is 3000rpm,
Time is 5-10min.
7. recovery method as claimed in claim 1, it is characterised in that described method particularly as follows:
(1) collect waste and old lithium ion battery, discharge completely；
(2) in the glove box of full inert gas, battery case is cut open, take out battery core, be placed in DMC
Soak 0.5～1h, and flush three times；
(3) battery core removing glove box, take out positive and negative plate, positive plate is soaked in NMP, negative pole
Sheet is soaked in distilled water；Transferring to the most together in supersonic cleaning machine, temperature furnishing 85 degree, with 200W
Hunting of frequency 10min；
(4) nmp solution after processing and distilled water are carried out distillation process, respectively obtain plus plate current-collecting body
With positive mix solution, negative current collector and negative pole powder solution；Gained plus plate current-collecting body and negative current collector
Recycle；
(5) align, negative pole powder solution washs after being centrifuged 5min with speed 3000rpm respectively, weight
Collect positive and negative electrode powder after multiple 3-5 time, then positive and negative electrode powder is placed in air dry oven with 100 DEG C
Toast and i.e. obtain positive and negative electrode recovery just material；
(6) positive pole reclaiming just material and be used for preparing new anode material for lithium-ion batteries, negative pole reclaims just expects system
Standby become carbon nanometer fragment, prepare for material with carbon element, tire carbon dope or iron and steel steel-making.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610284928.6A CN105870529A (en) | 2016-05-03 | 2016-05-03 | Recovery method for waste lithium ion batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610284928.6A CN105870529A (en) | 2016-05-03 | 2016-05-03 | Recovery method for waste lithium ion batteries |
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| CN105870529A true CN105870529A (en) | 2016-08-17 |
Family
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| CN201610284928.6A Pending CN105870529A (en) | 2016-05-03 | 2016-05-03 | Recovery method for waste lithium ion batteries |
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Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106129522A (en) * | 2016-08-31 | 2016-11-16 | 合肥国轩高科动力能源有限公司 | A kind of preparation method utilizing lithium ion battery negative to reclaim graphite |
| CN107317064A (en) * | 2017-06-22 | 2017-11-03 | 中南大学 | A kind of recovery method of waste lithium cell |
| CN107742760A (en) * | 2017-09-26 | 2018-02-27 | 北京矿冶研究总院 | Method for extracting lithium from waste lithium ion battery |
| CN107946686A (en) * | 2017-11-09 | 2018-04-20 | 合肥国轩高科动力能源有限公司 | A kind of waste and old lithium ion battery recovery method |
| CN108199105A (en) * | 2017-12-27 | 2018-06-22 | 同济大学 | The supersonic, water-heating separating technology of electrode component materials of used lithium batteries |
| CN108336429A (en) * | 2018-01-26 | 2018-07-27 | 合肥国轩高科动力能源有限公司 | A kind of regeneration method of disabled lithium ion cell positive active material |
| CN108760586A (en) * | 2018-05-23 | 2018-11-06 | 广州能源检测研究院 | A kind of method that overlay material particle size is distributed in detection lithium battery pole slice |
| CN108808153A (en) * | 2018-07-10 | 2018-11-13 | 东莞市丹斯迪新能源有限公司 | A kind of anode slice of lithium ion battery recovery and treatment method |
| CN108923096A (en) * | 2018-09-10 | 2018-11-30 | 厦门理工学院 | A kind of recycling of waste and old lithium ion battery cathode full constituent and regeneration method |
| CN109193064A (en) * | 2018-10-31 | 2019-01-11 | 中南大学 | A kind of method of waste power lithium battery valuable constituent sorting recycling |
| CN109244586A (en) * | 2018-10-24 | 2019-01-18 | 北京工业大学 | A kind of waste and old power battery environmental protection recycling and reusing method |
| CN110323510A (en) * | 2019-04-18 | 2019-10-11 | 深圳市伟创源科技有限公司 | A method of ferric phosphate lithium cell is regenerated using waste and old lithium ion battery |
| CN111326810A (en) * | 2018-12-13 | 2020-06-23 | 多氟多化工股份有限公司 | Method for photocatalytic degradation of organic matters in waste lithium ion battery pole piece and recovery method of current collector and active substances in pole piece |
| CN111900508A (en) * | 2020-07-30 | 2020-11-06 | 安徽绿沃循环能源科技有限公司 | Method for recycling decommissioned ternary batteries |
| CN112614971A (en) * | 2020-12-16 | 2021-04-06 | 东莞市和鸿升新材料科技有限公司 | Recycling method of retired lithium ion battery negative electrode material |
| CN112670612A (en) * | 2020-12-22 | 2021-04-16 | 东莞市和鸿升新材料科技有限公司 | Method for preparing recycled pole piece regenerated negative electrode material by wet separation |
| CN112768796A (en) * | 2020-12-30 | 2021-05-07 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Method for treating waste lithium battery |
| CN112952230A (en) * | 2021-03-01 | 2021-06-11 | 芜湖天弋能源科技有限公司 | Recovery method of waste 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 |
| CN114345539A (en) * | 2021-12-31 | 2022-04-15 | 湖南江冶新能源科技股份有限公司 | Method for separating anode powder and cathode powder of waste lithium battery |
| CN114361634A (en) * | 2022-01-05 | 2022-04-15 | 华中科技大学 | Efficient stripping method for battery positive/negative electrode material |
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Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106129522A (en) * | 2016-08-31 | 2016-11-16 | 合肥国轩高科动力能源有限公司 | A kind of preparation method utilizing lithium ion battery negative to reclaim graphite |
| CN107317064A (en) * | 2017-06-22 | 2017-11-03 | 中南大学 | A kind of recovery method of waste lithium cell |
| CN107742760A (en) * | 2017-09-26 | 2018-02-27 | 北京矿冶研究总院 | Method for extracting lithium from waste lithium ion battery |
| CN107946686A (en) * | 2017-11-09 | 2018-04-20 | 合肥国轩高科动力能源有限公司 | A kind of waste and old lithium ion battery recovery method |
| CN108199105A (en) * | 2017-12-27 | 2018-06-22 | 同济大学 | The supersonic, water-heating separating technology of electrode component materials of used lithium batteries |
| CN108336429A (en) * | 2018-01-26 | 2018-07-27 | 合肥国轩高科动力能源有限公司 | A kind of regeneration method of disabled lithium ion cell positive active material |
| CN108760586A (en) * | 2018-05-23 | 2018-11-06 | 广州能源检测研究院 | A kind of method that overlay material particle size is distributed in detection lithium battery pole slice |
| CN108808153A (en) * | 2018-07-10 | 2018-11-13 | 东莞市丹斯迪新能源有限公司 | A kind of anode slice of lithium ion battery recovery and treatment method |
| CN108923096B (en) * | 2018-09-10 | 2020-05-19 | 厦门理工学院 | Method for recycling and regenerating all components of negative electrode of waste lithium ion battery |
| CN108923096A (en) * | 2018-09-10 | 2018-11-30 | 厦门理工学院 | A kind of recycling of waste and old lithium ion battery cathode full constituent and regeneration method |
| CN109244586A (en) * | 2018-10-24 | 2019-01-18 | 北京工业大学 | A kind of waste and old power battery environmental protection recycling and reusing method |
| CN109244586B (en) * | 2018-10-24 | 2021-03-30 | 北京工业大学 | Environment-friendly recycling method for waste power batteries |
| CN109193064A (en) * | 2018-10-31 | 2019-01-11 | 中南大学 | A kind of method of waste power lithium battery valuable constituent sorting recycling |
| CN111326810B (en) * | 2018-12-13 | 2021-08-13 | 多氟多新材料股份有限公司 | Method for photocatalytic degradation of organic matters in waste lithium ion battery pole piece and recovery method of current collector and active substances in pole piece |
| CN111326810A (en) * | 2018-12-13 | 2020-06-23 | 多氟多化工股份有限公司 | Method for photocatalytic degradation of organic matters in waste lithium ion battery pole piece and recovery method of current collector and active substances in pole piece |
| CN110323510A (en) * | 2019-04-18 | 2019-10-11 | 深圳市伟创源科技有限公司 | A method of ferric phosphate lithium cell is regenerated using waste and old lithium ion battery |
| CN111900508A (en) * | 2020-07-30 | 2020-11-06 | 安徽绿沃循环能源科技有限公司 | Method for recycling decommissioned ternary batteries |
| CN112614971A (en) * | 2020-12-16 | 2021-04-06 | 东莞市和鸿升新材料科技有限公司 | Recycling method of retired lithium ion battery negative electrode material |
| CN112670612A (en) * | 2020-12-22 | 2021-04-16 | 东莞市和鸿升新材料科技有限公司 | Method for preparing recycled pole piece regenerated negative electrode material by wet separation |
| CN112768796A (en) * | 2020-12-30 | 2021-05-07 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Method for treating waste lithium battery |
| CN112952230A (en) * | 2021-03-01 | 2021-06-11 | 芜湖天弋能源科技有限公司 | Recovery method of waste 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 |
| CN114345539A (en) * | 2021-12-31 | 2022-04-15 | 湖南江冶新能源科技股份有限公司 | Method for separating anode powder and cathode powder of waste lithium battery |
| CN114361634A (en) * | 2022-01-05 | 2022-04-15 | 华中科技大学 | Efficient stripping method for battery positive/negative electrode material |
| CN114361634B (en) * | 2022-01-05 | 2023-04-18 | 华中科技大学 | Efficient stripping method for battery positive/negative electrode material |
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Application publication date: 20160817 |