CN108232352A - A kind of reclaimer and method of lithium-ion battery lithium iron phosphate positive electrode - Google Patents
A kind of reclaimer and method of lithium-ion battery lithium iron phosphate positive electrode Download PDFInfo
- Publication number
- CN108232352A CN108232352A CN201810087970.8A CN201810087970A CN108232352A CN 108232352 A CN108232352 A CN 108232352A CN 201810087970 A CN201810087970 A CN 201810087970A CN 108232352 A CN108232352 A CN 108232352A
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- China
- Prior art keywords
- lithium
- ion battery
- positive electrode
- iron phosphate
- babinet
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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 discloses a kind of reclaimers of lithium-ion battery lithium iron phosphate positive electrode, including sheet clipping machine, dissolving tank, drying box, filter device, Suction filtration device, dryer, ball mill, screening plant and annealing device, the sheet clipping machine is connected successively with dissolving tank and filter device, the filter device is connected respectively with drying box and Suction filtration device, the Suction filtration device is connected successively with dryer, ball mill, screening plant and annealing device, this reclaimer process is simple and efficient, and will not generate secondary pollution;While positive mix is recycled, the aluminium foil by-product that cleanliness factor is preferable, has certain economic value also can obtain;The positive mix of recycling has good processing performance, and through the heat treatment reparation under certain condition, can keep higher specific discharge capacity and good cyclical stability.Electrochemical property test is carried out to the positive mix of recycling, the results showed that its discharge capacity is up to 160mAh/g, and capacity retention ratio is more than 95% after 300 cycles.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries recovery technology field, specific field is a kind of lithium ion battery phosphoric acid
The reclaimer and method of iron lithium anode material.
Background technology
In recent years, flourishing with New Energy Industry drives lithium ion battery industry fast-developing, lithium ion battery
It is widely used in the fields such as mobile electronic device, new-energy automobile and large-scale energy storage device at present.Lithium ion battery usage amount
Increase will necessarily generate a large amount of waste and old batteries, how correctly and efficiently using this part old and useless battery become one it is to be solved
The problem of.The processing of waste and old lithium ion battery mainly recycles wherein valuable material, and handling proper will generate can
The economic benefit of sight, deals with improperly, the problems such as generating waste and environmental pollution.Therefore, this patent is directed to current usage amount very
The lithium ion battery of big phosphoric acid iron lithium anode material, using a kind of recovery method of positive electrode, to search out one kind
The method of the effective recycling of waste lithium ion cell anode material.
Invention content
The purpose of the present invention is to provide a kind of reclaimer and method of lithium-ion battery lithium iron phosphate positive electrode, with
Solve the problems mentioned above in the background art.
To achieve the above object, the present invention provides following technical solution:A kind of lithium-ion battery lithium iron phosphate positive electrode
Reclaimer, including sheet clipping machine, dissolving tank, drying box, filter device, Suction filtration device, dryer, ball mill, screening plant
And annealing device, the sheet clipping machine are connected successively with dissolving tank and filter device, the filter device respectively with drying box and
Suction filtration device is connected, and the Suction filtration device is connected successively with dryer, ball mill, screening plant and annealing device, described dry
Dry case includes babinet and case lid, and the intracavity bottom of the babinet is uniformly provided with heating element, and the side wall middle part of the babinet is uniformly
Equipped with venthole, the inner cavity of the babinet is movably installed with partition board, and electric expansion is fixedly connected in the middle part of the lower end of the partition board
One end of bar, the other end of the electric telescopic rod are fixedly connected with the cabinets cavity bottom, and the upper end of the partition board is symmetrical
It is fixedly connected with one end of strut, the lower surface of the other end of the strut with the case lid is fixedly connected, the case lid
Upper end connection is equipped with exhaust outlet, and the top of the exhaust outlet is equipped with electric machine support, and the electric machine support is equipped with motor, institute
The output terminal for stating motor is equipped with flabellum, and the side wall of the babinet is equipped with controller, and the controller passes through electric conductor point
It Lian Jie not heating element, electric telescopic rod and motor.
Preferably, the lower end of the babinet is equipped with bottom plate, and the lower end of the bottom plate is equipped with idler wheel.
Preferably, the heating element is PTC heating elements.
Preferably, insulating layer, water accepting layer and filter layer have been sequentially filled except interior in the venthole.
Preferably, the partition board is made of ceramic material.
Preferably, the recovery method of the lithium-ion battery lithium iron phosphate positive electrode is as follows:
(1)Broken small pieces are cut into after the discarded anode pole piece that generation is disassembled to obtain or produced from waste lithium cell is collected;
(2)It is 1 that fractionlet is added in volume ratio:In 1 DMF and the mixed liquor of water(Cost is relatively low and safety is good), stirring 1.5
A hour so that the PVDF bonding agents on anode pole piece are dissolved in DMF solution, while positive mix comes off from aluminium foil, into
Enter in solution;
(3)Solution is filtered, aluminium foil fragment is obtained, then aluminium foil is dried, directly obtains aluminium foil reclaimed materials;
(4)The filtrate being obtained by filtration in step 3 is filtered, obtains sediment powder, is dried at 70 DEG C, is obtained just
The positive mix of step;
(5)Obtained positive mix 30 minutes ball millings of progress will be filtered, sieved after 400 mesh to get LiFePO4 positive mixs
(LiFePO4 and conductive agent mixed black toner material);
(6)The mixed powder of obtained LiFePO4 and conductive agent are heat-treated, condition is nitrogen protection atmosphere, at 200 DEG C
Heat treatment 1 hour.
Compared with prior art, the beneficial effects of the invention are as follows:Anode pole piece can be carried out by sheet clipping machine to shred processing,
The PVDF bonding agents on the anode pole piece that shreds can be dissolved in DMF solution by dissolving tank, while positive mix is from aluminium foil
On come off, into solution, the aluminium foil in solution can be recycled, passed through by filter device and being equipped with for drying box
Suction filtration device, dryer, ball mill, screening plant and being equipped with for annealing device can carry out the LiFePO4 in solution
Recycling, this reclaimer process are simple and efficient, and will not generate secondary pollution;While positive mix is recycled, also it can obtain clean
Cleanliness is preferable, has the aluminium foil by-product of certain economic value;The positive mix of recycling has good processing performance, and through one
Heat treatment reparation under fixed condition can keep higher specific discharge capacity and good cyclical stability.To the positive powder of recycling
Material carries out electrochemical property test, the results showed that its discharge capacity is up to 160mAh/g, and capacity retention ratio is big after 300 cycles
In 95%.
Description of the drawings
Fig. 1 is the system structure diagram of the present invention;
Fig. 2 is the structure diagram of drying box in the present invention;
Fig. 3 is the flow chart of recovery method of the present invention.
In figure:1- sheet clipping machines, 2- dissolving tanks, 3- filter devices, 4- drying boxes, 401- babinets, 402- case lids, 403- heating
Element, 404- ventholes, 405- partition boards, 406- electric telescopic rods, 407- struts, 408- exhaust outlets, 409- electric machine supports, 410-
Motor, 411- flabellums, 412- controllers, 413- bottom plates, 414- idler wheels, 5- Suction filtration devices, 6- dryers, 7- ball mills, 8-
Screening plant, 9- annealing devices.
Specific embodiment
Below in conjunction with the attached drawing in the embodiment of the present invention, the technical solution in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other without making creative work
Embodiment shall fall within the protection scope of the present invention.
Referring to Fig. 1, the present invention provides a kind of technical solution:A kind of recycling of lithium-ion battery lithium iron phosphate positive electrode
Equipment, including sheet clipping machine 1, dissolving tank 2, drying box 3, filter device 4, Suction filtration device 5, dryer 6, ball mill 7, screening plant
8 and annealing device 9, sheet clipping machine to the anode pole piece of recycling shred processing, the sheet clipping machine successively with dissolving tank and mistake
Filter device is connected, and it is 1 that the anode pole piece after shredding, which is positioned in dissolving tank and adds in volume ratio,:In 1 DMF and the mixed liquor of water
(Cost is relatively low and safety is good), stirring 1.5 hours so that and the PVDF bonding agents on anode pole piece are dissolved in DMF solution,
Positive mix comes off from aluminium foil simultaneously, and into solution, the filter device is connected respectively with drying box and Suction filtration device, will
Solution filters, and obtains aluminium foil fragment, then aluminium foil is dried, and directly obtains aluminium foil reclaimed materials, the Suction filtration device according to
It is secondary to be connected with dryer, ball mill, screening plant and annealing device, the filtrate being obtained by filtration in step filter device is taken out
Filter, obtains sediment powder, is dried at 70 DEG C, obtain preliminary positive mix;To filter obtained positive mix into
30 minutes ball millings of row are sieved after 400 mesh to get LiFePO4 positive mixs(LiFePO4 and conductive agent mixed black toner material);It will
Obtained LiFePO4 and the mixed powder of conductive agent is heat-treated, and condition is nitrogen protection atmosphere, and it is small to be heat-treated 1 at 200 DEG C
When, the drying box includes babinet 401 and case lid 402, and the intracavity bottom of the babinet is uniformly provided with heating element 403, heats
Element provides temperature control for the internal environment of drying box, and venthole 404 is uniformly provided in the middle part of the side wall of the babinet, extraneous
Gas can be closely humiliated in drying box by venthole, and the inner cavity of the babinet is movably installed with partition board 405, is used to place band on partition board
Dry aluminium foil fragment, and it is prevented to be in direct contact with heating element, it is fixedly connected with electronic stretch in the middle part of the lower end of the partition board
One end of contracting bar 406, the other end of the electric telescopic rod are fixedly connected with the cabinets cavity bottom, and electric telescopic rod is stretched
It is long in the vertical direction to be moved with dynamic dividing plate and case lid with shortening action, partition board is made to stretch out babinet convenient to placing or taking thereon
Aluminium foil is taken, the upper end of the partition board is symmetrically fixedly connected with one end of strut 407, and strut ensure that case lid moves together with partition board
Dynamic, the lower surface of the other end of the strut with the case lid is fixedly connected, and the upper end connection of the case lid is equipped with exhaust
Mouth 408, moist gas are discharged by exhaust outlet outside babinet, and the top of the exhaust outlet is equipped with electric machine support 409, the motor branch
Frame is equipped with motor 410, electric machine support fixed motor, and the output terminal of the motor is equipped with flabellum 411, and motor turns
Dynamic that flabellum is driven to rotate and then the gas circulation in babinet is made aluminium foil to be dried processing, the side wall of the babinet is equipped with
Controller 412, the controller are connected heating element, electric telescopic rod and motor by electric conductor, pass through controller respectively
Control the heating temperature of heating element and the work of electric telescopic rod and motor.
Specifically, the lower end of the babinet is equipped with bottom plate 413, the lower end of the bottom plate is equipped with idler wheel 414, convenient to dress
It is moved between putting.
Specifically, the heating element is PTC heating elements, heating effect is more preferable.
Specifically, being sequentially filled insulating layer, water accepting layer and filter layer except interior in the venthole, insulating layer is prevented
The heat that only heating element generates distributes, and water accepting layer prevents the steam in the external world from entering the inside of babinet by venthole, and filter layer is prevented
Only extraneous dust particale enters box house.
Specifically, the partition board is made of ceramic material, ceramic heat conductivility is more preferable.
Specifically, the recovery method of the lithium-ion battery lithium iron phosphate positive electrode is as follows:
(1)Broken small pieces are cut into after the discarded anode pole piece that generation is disassembled to obtain or produced from waste lithium cell is collected;
(2)It is 1 that fractionlet is added in volume ratio:In 1 DMF and the mixed liquor of water(Cost is relatively low and safety is good), stirring 1.5
A hour so that the PVDF bonding agents on anode pole piece are dissolved in DMF solution, while positive mix comes off from aluminium foil, into
Enter in solution;
(3)Solution is filtered, aluminium foil fragment is obtained, then aluminium foil is dried, directly obtains aluminium foil reclaimed materials;
(4)The filtrate being obtained by filtration in step 3 is filtered, obtains sediment powder, is dried at 70 DEG C, is obtained just
The positive mix of step;
(5)Obtained positive mix 30 minutes ball millings of progress will be filtered, sieved after 400 mesh to get LiFePO4 positive mixs
(LiFePO4 and conductive agent mixed black toner material);
(6)The mixed powder of obtained LiFePO4 and conductive agent are heat-treated, condition is nitrogen protection atmosphere, at 200 DEG C
Heat treatment 1 hour.
Operation principle:It is shredded by the recycling from old and useless battery or by the anode leftover pieces that production generates, adds in DMF and water
Solution in stir, filtered after a period of time, in the process, the bonding agent PVDF on positive plate will be dissolved in DMF solution,
Positive electrode particle powder will come off from aluminium foil, until forming suspension in solution.This solution is separated by filtration, the solid precipitated
Aluminum foil material and the suspension containing positive mix.Isolated solid aluminium foil can directly recycle profit through further washing, drying
With.Suspension is filtered, then obtained sediment is dried, ball milling and sieving processing, obtains LiFePO4 positive powders
Material(Contain partially electronically conductive dose), finally it is heat-treated under certain condition, obtains anode reclaimed materials.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (6)
1. a kind of reclaimer of lithium-ion battery lithium iron phosphate positive electrode, including sheet clipping machine(1), dissolving tank(2), drying box
(3), filter device(4), Suction filtration device(5), dryer(6), ball mill(7), screening plant(8)And annealing device(9),
It is characterized in that:The sheet clipping machine(1)Successively with dissolving tank(2)And filter device(3)It is connected, the filter device(3)Respectively with
Drying box(4)And Suction filtration device(5)It is connected, the Suction filtration device(5)Successively with dryer(6), ball mill(7), screening plant
(8)And annealing device(9)It is connected, the drying box(4)Including babinet(401)And case lid(402), the babinet(401)'s
Intracavity bottom is uniformly provided with heating element(403), the babinet(401)Side wall in the middle part of be uniformly provided with venthole(404), it is described
Babinet(401)Inner cavity be movably installed with partition board(405), the partition board(405)Lower end in the middle part of be fixedly connected with electric expansion
Bar(406)One end, the electric telescopic rod(406)The other end and the babinet(401)Intracavity bottom is fixedly connected, described
Partition board(405)Upper end be symmetrically fixedly connected with strut(407)One end, the strut(407)The other end with the case
Lid(402)Lower surface be fixedly connected, the case lid(402)Upper end connection exhaust outlet is installed(408), the exhaust outlet
(408)Top be equipped with electric machine support(409), the electric machine support(409)It is equipped with motor(410), the motor
(410)Output terminal flabellum is installed(411), the babinet(401)Side wall be equipped with controller(412), the controller
(412)Heating element is connected by electric conductor respectively(403), electric telescopic rod(406)And motor(410).
2. a kind of reclaimer of lithium-ion battery lithium iron phosphate positive electrode according to claim 1, it is characterised in that:
The babinet(401)Lower end be equipped with bottom plate(413), the bottom plate(413)Lower end be equipped with idler wheel(414).
3. a kind of reclaimer of lithium-ion battery lithium iron phosphate positive electrode according to claim 1, it is characterised in that:
The heating element(403)For PTC heating elements.
4. a kind of reclaimer of lithium-ion battery lithium iron phosphate positive electrode according to claim 1, it is characterised in that:
The venthole(404)In be sequentially filled insulating layer, water accepting layer and filter layer except interior.
5. a kind of reclaimer of lithium-ion battery lithium iron phosphate positive electrode according to claim 1, it is characterised in that:
The partition board(405)It is made of ceramic material.
6. a kind of recovery method of lithium-ion battery lithium iron phosphate positive electrode according to claim 1, it is characterised in that:
The recovery method of the lithium-ion battery lithium iron phosphate positive electrode is as follows:
(1)Broken small pieces are cut into after the discarded anode pole piece that generation is disassembled to obtain or produced from waste lithium cell is collected;
(2)It is 1 that fractionlet is added in volume ratio:In 1 DMF and the mixed liquor of water(Cost is relatively low and safety is good), stirring 1.5
A hour so that the PVDF bonding agents on anode pole piece are dissolved in DMF solution, while positive mix comes off from aluminium foil, into
Enter in solution;
(3)Solution is filtered, aluminium foil fragment is obtained, then aluminium foil is dried, directly obtains aluminium foil reclaimed materials;
(4)The filtrate being obtained by filtration in step 3 is filtered, obtains sediment powder, is dried at 70 DEG C, is obtained just
The positive mix of step;
(5)Obtained positive mix 30 minutes ball millings of progress will be filtered, sieved after 400 mesh to get LiFePO4 positive mixs
(LiFePO4 and conductive agent mixed black toner material);
(6)The mixed powder of obtained LiFePO4 and conductive agent are heat-treated, condition is nitrogen protection atmosphere, at 200 DEG C
Heat treatment 1 hour.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN109713393A (en) * | 2018-12-30 | 2019-05-03 | 沈阳化工研究院有限公司 | A kind of isolated method of lithium battery active material |
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CN105355998A (en) * | 2015-11-03 | 2016-02-24 | 百顺松涛(天津)动力电池科技发展有限公司 | Recovery method of LiFePO4 positive electrode material |
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 |
CN206919554U (en) * | 2017-06-21 | 2018-01-23 | 无锡市跨克微营养素有限公司 | Double-layer explosion-proof destatics powder materials drying baker |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN204177138U (en) * | 2014-09-10 | 2015-02-25 | 浙江朗博药业有限公司 | A kind of adjustable angle heated-air circulation oven |
CN105355998A (en) * | 2015-11-03 | 2016-02-24 | 百顺松涛(天津)动力电池科技发展有限公司 | Recovery method of LiFePO4 positive electrode material |
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 |
CN206919554U (en) * | 2017-06-21 | 2018-01-23 | 无锡市跨克微营养素有限公司 | Double-layer explosion-proof destatics powder materials drying baker |
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CN109713393A (en) * | 2018-12-30 | 2019-05-03 | 沈阳化工研究院有限公司 | A kind of isolated method of lithium battery active material |
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