CN109290339A - A kind of method of positive pole powder and aluminium collector in separating waste, worn tertiary cathode piece - Google Patents
A kind of method of positive pole powder and aluminium collector in separating waste, worn tertiary cathode piece Download PDFInfo
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- CN109290339A CN109290339A CN201811050710.XA CN201811050710A CN109290339A CN 109290339 A CN109290339 A CN 109290339A CN 201811050710 A CN201811050710 A CN 201811050710A CN 109290339 A CN109290339 A CN 109290339A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/0038—Obtaining aluminium by other processes
- C22B21/0069—Obtaining aluminium by other processes from scrap, skimmings or any secondary source aluminium, e.g. recovery of alloy constituents
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
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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
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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
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- Environmental & Geological Engineering (AREA)
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- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of methods of positive pole powder and aluminium collector in separating waste, worn tertiary cathode piece to be placed in pyrolysis furnace method includes the following steps: waste and old tertiary cathode piece is crushed, and in atmosphere of inert gases, anaerobic cracking is carried out at 450~550 DEG C；Positive plate after cracking is subjected to second-time breakage, screening, oversize is aluminium collector, and screenings is positive pole powder；Aluminium collector is subjected to pneumatic separation, obtains positive pole powder and pure aluminium collector.The method of the present invention is using waste and old tertiary cathode piece as raw material, positive pole powder and aluminium collector in the method separation pole piece combined using anaerobic cracking and pneumatic separation, have many advantages, such as that positive pole powder separates thorough, environmental-friendly, simple process, easy to operate, high production efficiency with aluminium collector, economic benefit is not only increased, environmental pollution is also reduced.The present invention can directly obtain metallic aluminium, and security risk is small, and economic value is high.
Description
Technical field
The invention belongs to lithium ion battery material recycling fields, and in particular in a kind of separating waste, worn tertiary cathode piece
The method of positive pole powder and aluminium collector.
Background technique
Lithium ion battery is that battery can be recycled in a kind of environment-friendly type, have energy density it is high, it is light-weight, small in size,
The features such as having extended cycle life, is without memory suffers from fields such as communication, medical treatment, traffic, space flight, energy storage and is widely applied.
In recent years, with the steady growth of the lithium ion battery market demand, lithium ion battery production capacity constantly expands, production and
Occur large quantities of lithium ion battery positive plates in use process, wherein waste and old nickel-cobalt-manganese ternary battery anode slice is that one kind contains
The higher industrial refuse product of cobalt, nickel also will cause environmental pollution if dealing with the waste for not only resulting in resource improperly.Therefore,
Recycle waste and old tertiary cathode piece to reduce environmental pollution, alleviate cobalt, nickel resources scarcity is of great significance.
The waste and old tertiary cathode piece method of processing of existing industrial application mainly includes recycling and the positive electrode of valuable metal
Regeneration, wherein positive pole powder and the separation of aluminium collector are committed steps in removal process, mainly use organic solvent at present
Dissolution method, alkali solution technique separate positive pole powder and aluminium collector.
Collector refers to the structure or part for collecting electric current.On lithium ion battery, aluminium collector is primarily referred to as aluminium foil.Just
Pole powder is a kind of mixture, and composition includes positive electrode, conductive agent and binder, because containing binder in positive pole powder,
So that aluminium collector and positive pole powder are closely linked, which can just decompose in 315 DEG C or more of high temperature, lose work
Property, so that the cohesive force between positive pole powder and aluminium collector is eliminated.
Chinese patent ZL 201410244425.7 discloses cobalt acid lithium and aluminium foil on a kind of scrap lithium ion battery positive plate
Separation method, positive plate calcined at 500-600 DEG C, sieved after adding water and stirring by this method, and oversize is aluminium foil, screenings warp
It is calcined again after crossing suction filtration, obtains cobalt acid lithium.The patent is using aerobic calcining, and aerobic calcining meeting is so that entire pyrolytic process
Chemically react uncontrollable, thermit reaction occurs for aluminium collector and positive active material, and aluminium can be transferred in positive active material,
After separating aluminium collector and positive pole powder, aluminium content is higher in positive pole powder, so bad using this method separating effect.In addition,
It is stirred using water, introduces a large amount of waste water, and the aluminium collector under high-temperature condition may react with water and generate hydrogen, draw
Hair accident, meanwhile, aluminium easily aoxidizes after entering water, reduces the economic value of aluminium.
Chinese patent application CN 106450557A discloses the positive electrode and aluminium of a kind of separating waste, worn anode on piece
Method, this method by positive plate under inert gas protection, 700-800 DEG C calcining, respectively obtained after screening microballoon containing aluminium and
Positive electrode.700-800 DEG C of the patent calcination temperature, the fusing point of aluminium are 660 DEG C, and aluminium is in molten state at this time, even if most
Aluminium enters porous material, but also has small part aluminium and positive pole powder tight, and aluminium content is too in the positive pole powder after being sieving through
Height is unfavorable for leaching.In addition, the porous material of the method is finally impregnated to obtain aluminum sulfate with sulfuric acid, a large amount of sulfuric acid can be expended, are generated
Hydrogen, and obtained aluminum sulfate solution does not have practical application value.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide positive powders in a kind of separating waste, worn tertiary cathode piece
The method at end and aluminium collector, it is thorough, environmental-friendly, easy to operate, raw that there is this method positive pole powder to separate with aluminium collector
The advantages that high-efficient is produced, there is great prospects for commercial application.
The purpose of the invention is achieved by the following technical solution:
A kind of method of positive pole powder and aluminium collector in separating waste, worn tertiary cathode piece, comprising the following steps:
(1) waste and old tertiary cathode piece is crushed, is placed in pyrolysis furnace, in atmosphere of inert gases, at 450~550 DEG C into
The cracking of row anaerobic；
It is based on considered below that the step, which uses the anaerobic cracking in inert atmosphere, and one is to ensure that chemical reaction is controllable, i.e.,
Aluminium collector is got along well, and oxygen reacts, aluminium collector discord nickle cobalt lithium manganate reacts；Two are to ensure that cracking occurs for binder pvdf instead
It should be the endothermic reaction without combustion reaction, cracking reaction, not will cause localized hyperthermia and aluminium collector fusing package occurring just
The case where pole powder；
According to the above two o'clock, confirm that calcination temperature is higher than pvdf cracking temperature, is lower than aluminium fusion temperature, that is, calcining temperature
Degree is greater than 315 DEG C, less than 660 DEG C；Real process does not melt completely in order to guarantee that pvdf cracks abundant, aluminium collector, so selection
Calcination temperature is 450~550 DEG C.
The time of the anaerobic cracking is 40~80min；
Described is broken, and broken positive plate length and width are 3~5cm；
(2) positive plate after cracking is subjected to second-time breakage, screening, oversize is aluminium collector, and screenings is positive powder
End；Aluminium collector is subjected to pneumatic separation, obtains positive pole powder and pure aluminium collector；
The second-time breakage, positive plate length and width are 1~2cm after being crushed；
The grit number of the screening is 80~120 mesh；
The pneumatic separation, the equipment of use are vertical airflow screen, throughput 500m3/ h, sieve mesh number 100~200
Mesh.
The method that the present invention originally uses anaerobic cracking and pneumatic separation to combine, separating waste, worn nickel-cobalt-manganese ternary is just
Pole piece positive pole powder and aluminium collector.The first step, the waste and old tertiary cathode piece of pyrolysis furnace heated at constant temperature is for a period of time under inert atmosphere；
Second step, carries out second-time breakage after the tertiary cathode piece after heating is taken out, screening obtains positive pole powder and aluminium collector；Third
Aluminium collector is carried out pneumatic separation, obtains positive pole powder and clean aluminium collector by step.The method positive pole powder and aluminium afflux
Body separation thoroughly, improves the rate of recovery of collector metal, and reduce the entrainment of aluminium in positive pole powder, is conducive to anode
The subsequent smelting recovery process of powder.
The present invention has the following advantages and effects with respect to the prior art:
The method of the present invention is divided using waste and old tertiary cathode piece as raw material using the method that anaerobic cracking and pneumatic separation combine
From positive pole powder in pole piece and aluminium collector, have positive pole powder separated with aluminium collector thorough, environmental-friendly, simple process,
The advantages that easy to operate, high production efficiency, economic benefit is not only increased, environmental pollution is also reduced.The present invention can be obtained directly
To metallic aluminium, security risk is small, and economic value is high.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
A kind of method of positive pole powder and aluminium collector in separating waste, worn tertiary cathode piece, comprising the following steps:
Waste and old nickel-cobalt-manganese ternary battery anode slice is broken into the fragment that length and width are 5cm, 500g fragment is weighed and is put into cracking
In furnace, opens pyrolysis furnace and set temperature is 450 DEG C, heated at constant temperature 60min in atmosphere of inert gases, take out positive plate and carry out two
It is secondary broken, aluminium collector and positive pole powder are sieved with 80 mesh standard sieves, aluminium collector is subjected to pneumatic separation with vertical airflow screen
Obtain positive pole powder and clean aluminium collector.
Obtaining nickel content remaining on aluminium collector with WFX-130A type atomic absorption spectrophotometer measurement is 0.86%,
Cobalt content is 0.47%, manganese content 0.33%；Aluminium content is 0.49% in positive pole powder.
Embodiment 2
A kind of method of positive pole powder and aluminium collector in separating waste, worn tertiary cathode piece, comprising the following steps:
The waste and old ternary battery anode slice fragment of 1000g is weighed, is put into pyrolysis furnace, pyrolysis furnace is opened and set temperature is
It 480 DEG C, heated at constant temperature 80min in atmosphere of inert gases, takes out positive plate and carries out second-time breakage, sieve aluminium with 100 mesh standard sieves
Aluminium collector is carried out pneumatic separation with vertical airflow screen and obtains positive pole powder and clean aluminium afflux by collector and positive pole powder
Body.
Obtaining nickel content remaining on aluminium collector with WFX-130A type atomic absorption spectrophotometer measurement is 0.79%,
Cobalt content is 0.42%, manganese content 0.30%；Aluminium content is 0.41% in positive pole powder.
Embodiment 3
A kind of method of positive pole powder and aluminium collector in separating waste, worn tertiary cathode piece, comprising the following steps:
The waste and old ternary battery anode slice fragment of 1000g is weighed, is put into pyrolysis furnace, pyrolysis furnace is opened and set temperature is
It 550 DEG C, heated at constant temperature 60min in atmosphere of inert gases, takes out positive plate and carries out second-time breakage, sieve aluminium collection with 80 mesh standard sieves
Aluminium collector is carried out pneumatic separation with vertical airflow screen and obtains positive pole powder and clean aluminium afflux by fluid and positive pole powder
Body.
Obtaining nickel content remaining on aluminium collector with WFX-130A type atomic absorption spectrophotometer measurement is 0.75%,
Cobalt content is 0.38%, manganese content 0.19%；Aluminium content is 0.37% in positive pole powder.
Embodiment 4
A kind of method of positive pole powder and aluminium collector in separating waste, worn tertiary cathode piece, comprising the following steps:
The waste and old ternary battery anode slice fragment of 500g is weighed, is put into pyrolysis furnace, pyrolysis furnace is opened and set temperature is 480
DEG C, heated at constant temperature 40min in atmosphere of inert gases takes out positive plate and carries out second-time breakage, sieves aluminium afflux with 120 mesh standard sieves
Aluminium collector is carried out pneumatic separation with vertical airflow screen and obtains positive pole powder and clean aluminium collector by body and positive pole powder.
Obtaining nickel content remaining on aluminium collector with WFX-130A type atomic absorption spectrophotometer measurement is 0.81%,
Cobalt content is 0.33%, manganese content 0.21%；Aluminium content is 0.24% in positive pole powder.
In conclusion the present invention is using in the method separating waste, worn tertiary cathode piece that anaerobic cracks and pneumatic separation combines
Positive pole powder and aluminium collector, positive pole powder separate thoroughly with aluminium collector, and the total residual volume of aluminium collector nickel cobalt manganese is 1.2% left
The right side, aluminium content is less than 0.5% in positive pole powder.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (6)
1. a kind of method of positive pole powder and aluminium collector in separating waste, worn tertiary cathode piece, it is characterised in that including following step
It is rapid:
(1) waste and old tertiary cathode piece is crushed, is placed in pyrolysis furnace, in atmosphere of inert gases, carry out nothing at 450~550 DEG C
Oxygen cracking；
(2) positive plate after cracking is subjected to second-time breakage, screening, oversize is aluminium collector, and screenings is positive pole powder；It will
Aluminium collector carries out pneumatic separation, obtains positive pole powder and pure aluminium collector.
2. according to the method described in claim 1, it is characterized by: the time of step (1) anaerobic cracking be 40~
80min。
3. according to the method described in claim 1, it is characterized by: being crushed described in step (1), broken positive plate length and width
For 3~5cm.
4. according to the method described in claim 1, it is characterized by: second-time breakage described in step (2), positive length of a film after being crushed
Width is 1~2cm.
5. according to the method described in claim 1, it is characterized by: the grit number of step (2) described screening is 80~120 mesh.
6. according to the method described in claim 1, it is characterized by: pneumatic separation described in step (2), the equipment of use are vertical
Formula airflow screen, throughput 500m3/ h, 100~200 mesh of sieve mesh number.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811050710.XA CN109290339A (en) | 2018-09-10 | 2018-09-10 | A kind of method of positive pole powder and aluminium collector in separating waste, worn tertiary cathode piece |
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| CN201811050710.XA CN109290339A (en) | 2018-09-10 | 2018-09-10 | A kind of method of positive pole powder and aluminium collector in separating waste, worn tertiary cathode piece |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110120560A (en) * | 2019-04-16 | 2019-08-13 | 福建常青新能源科技有限公司 | A kind of waste and old ternary lithium battery recycling sorting process |
| CN112111649A (en) * | 2020-09-21 | 2020-12-22 | 天齐锂业（江苏）有限公司 | Method for recovering valuable metals in lithium ion battery |
| CN113909273A (en) * | 2021-12-07 | 2022-01-11 | 中国科学院过程工程研究所 | Waste lithium battery pole piece recovery method and application |
| CN113948788A (en) * | 2021-10-15 | 2022-01-18 | 广东瑞科美电源技术有限公司 | Lithium cobaltate positive electrode material and regeneration and repair method and application thereof |
| CN113943020A (en) * | 2021-10-15 | 2022-01-18 | 广东瑞科美电源技术有限公司 | Regenerated lithium cobaltate and activation method and application thereof |
| CN113943021A (en) * | 2021-10-15 | 2022-01-18 | 广东瑞科美电源技术有限公司 | Regenerated lithium cobaltate and repairing method and application thereof |
| CN114006070A (en) * | 2021-10-31 | 2022-02-01 | 湖南江冶机电科技股份有限公司 | Method for high-temperature pyrolysis and aerodynamic stripping and sorting of waste lithium batteries |
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| CN103915661A (en) * | 2013-01-09 | 2014-07-09 | 中国科学院过程工程研究所 | Method for direct recovery and restoration of lithium ion battery positive electrode material |
| CN108023091A (en) * | 2016-10-31 | 2018-05-11 | 荆门市格林美新材料有限公司 | The reproduction process of Vehicular dynamic battery nickel cobalt lithium aluminate cathode material |
| CN207398307U (en) * | 2017-11-13 | 2018-05-22 | 中国恩菲工程技术有限公司 | The processing system of waste and old lithium ion battery |
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| CN103915661A (en) * | 2013-01-09 | 2014-07-09 | 中国科学院过程工程研究所 | Method for direct recovery and restoration of lithium ion battery positive electrode material |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110120560A (en) * | 2019-04-16 | 2019-08-13 | 福建常青新能源科技有限公司 | A kind of waste and old ternary lithium battery recycling sorting process |
| CN112111649A (en) * | 2020-09-21 | 2020-12-22 | 天齐锂业（江苏）有限公司 | Method for recovering valuable metals in lithium ion battery |
| CN112111649B (en) * | 2020-09-21 | 2022-06-21 | 天齐锂业（江苏）有限公司 | Method for recovering valuable metals in lithium ion battery |
| CN113948788A (en) * | 2021-10-15 | 2022-01-18 | 广东瑞科美电源技术有限公司 | Lithium cobaltate positive electrode material and regeneration and repair method and application thereof |
| CN113943020A (en) * | 2021-10-15 | 2022-01-18 | 广东瑞科美电源技术有限公司 | Regenerated lithium cobaltate and activation method and application thereof |
| CN113943021A (en) * | 2021-10-15 | 2022-01-18 | 广东瑞科美电源技术有限公司 | Regenerated lithium cobaltate and repairing method and application thereof |
| CN113948788B (en) * | 2021-10-15 | 2023-11-03 | 广东瑞科美电源技术有限公司 | Lithium cobalt oxide positive electrode material and regeneration and repair method and application thereof |
| CN114006070A (en) * | 2021-10-31 | 2022-02-01 | 湖南江冶机电科技股份有限公司 | Method for high-temperature pyrolysis and aerodynamic stripping and sorting of waste lithium batteries |
| CN113909273A (en) * | 2021-12-07 | 2022-01-11 | 中国科学院过程工程研究所 | Waste lithium battery pole piece recovery method and application |
| 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 |
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