CN109536713A - A method of utilizing ionic liquid separating waste, worn active substance of lithium ion battery anode and aluminium foil - Google Patents
A method of utilizing ionic liquid separating waste, worn active substance of lithium ion battery anode and aluminium foil Download PDFInfo
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- CN109536713A CN109536713A CN201811392957.XA CN201811392957A CN109536713A CN 109536713 A CN109536713 A CN 109536713A CN 201811392957 A CN201811392957 A CN 201811392957A CN 109536713 A CN109536713 A CN 109536713A
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- Prior art keywords
- ionic liquid
- aluminium foil
- lithium ion
- ion battery
- active substance
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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
- 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
- C22B7/006—Wet 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
Abstract
The invention belongs to secondary resource utilization technology fields, it is related to a kind of method using ionic liquid separating waste, worn active substance of lithium ion battery anode and aluminium foil, it include: that the lithium ion battery positive plate after dismantling, sorting is put into ionic liquid, supersonic oscillations, stand at normal temperature；Aluminium foil is taken out, ionic liquid and black solid powder are separated by filtration；Ionic liquid is subjected to purifying drying process, obtains the ionic liquid that can be recycled；Black solid powder is dried, the raw material that can be used as extraction process Call Provision, nickel, manganese, lithium metal element is obtained.Method provided by the invention is increased the penetration power of ionic liquid by the cavitation of ultrasonic wave, is substantially increased the separative efficiency of positive active material and aluminium foil using intensified by ultrasonic wave ionic liquid separation positive active material and aluminium foil；Have many advantages, such as that the time is short, temperature is low, process flow is simple, easily controllable and amplification has potential using value.
Description
Technical field
The invention belongs to secondary resource utilization technology fields, and in particular to a kind of to utilize ionic liquid separating waste, worn lithium
The method of ion battery positive active material and aluminium foil.
Background technique
Lithium ion battery due to its energy density is high, capacity is big, the service life is long and it is without memory the advantages that, from 90 years 20th century
Since generation commercialization, it is widely used to the portable electronic products such as battery of mobile phone, laptop electric power field.In recent years by
In increasing substantially for new-energy automobile volume of production and marketing, power battery in 2016 has evolved into the highest production of consumption proportion in lithium battery
Product, it is contemplated that new-energy automobile power battery will enter scale retirement phase in 2018.China has become lithium-ion electric at present
Pond production, consumption and big export country.To promote the waste and old power accumulator of new-energy automobile to comprehensively utilize industrial scale, standardization
And professional development, improve waste and old power battery level of comprehensive utilization, country has issued that " new-energy automobile scraps old power electric power storage
Pond comprehensively utilizes industry standard condition ", it proposes to carry out the resource regeneration technology of positive and negative pole material, diaphragm, electrolyte etc., set
Standby, technique research and development and application improve coherent element regeneration level in waste and old power battery, wherein hydrometallurgy condition
Under, nickel, cobalt, manganese comprehensive recovery be not less than 98%；Under the conditions of pyrometallurgical smelting, nickel, rare earth comprehensive yield be not less than 97%.
Lithium ion battery is mainly made of shell, anode, cathode, diaphragm, electrolyte etc., positive and negative electrode mainly contain nickel,
The valuable metals resource such as cobalt, manganese, lithium, copper, aluminium, wherein cobalt is the rare strategy metal in China, and China is needed largely every year from state
Outer import.Such as cobalt accounts for 5~20% in ternary material battery positive electrode, and nickel accounts for 5~12%, and manganese accounts for 7~10%, and lithium accounts for 2~
5%.Electrolyte is mainly the lithium-containing compounds such as lithium hexafluoro phosphate and organic solvent, if these discarded lithium ion batteries obtain not
It is disposed to suitable, heavy metal ion and toxic, strong corrosive electrolyte in lithium battery etc. will likely cause serious environment
Pollution, while the waste that also will cause resource is lost.If these valuable metal resources of energy high efficiente callback, will generate good warp
Ji and social benefit, realize the sustainable development of resource.
The main method of waste and old lithium ion battery recycling at present has pyrogenic process and wet process, and compared with pyrogenic process, wet process has many
" three wastes " generated during advantage, such as wet-treating are less, while the metal product of available high-purity.Hydrometallurgic recovery
Key step include: electric discharge and dismantling, pretreatment, leaching, extraction and separation, wherein pretreatment seek to realize active material with
The separation of current collector aluminum foil is one of the committed step of waste lithium cell recycling.B.Scrosati etc., which is reported, utilizes N- methyl
The method that pyrrolidones (NMP) separates aluminium foil and positive electrode, aluminium foil recycles with metallic forms, by can be directly sharp again after processing
With, positive active material by acidleach, chemical precipitation cobalt hydroxide, high temperature prepare cobalt acid lithium (J.Power Sources, 2001,
92,65-69).This method dissolves Kynoar according to " similar compatibility " principle, using NMP etc. more highly polar organic solvent
(PVDF) binders, to realize the separation of positive active material and aluminium foil such as.This method is easy to operate, effectively increases separation
Efficiency is lost larger, while there is also rings since molecular solvent has the characteristics that volatile, inflammable in high temperature leaching process
The hidden danger in border and secure context.Chinese patent (patent No.: ZL201010262498.2) discloses a kind of molten using sodium hydroxide
Aluminium foil is solved, realizes the method that aluminium foil is separated with positive electrode, then recycle cobalt resource by processes such as acidleach, extractions.This method
A large amount of aluminium elements are introduced in subsequent extraction process, increase the difficulty of the metal extractions separating technology such as cobalt, while alkali soluble process
It is middle to generate a large amount of waste water.
Summary of the invention
The present invention separates on existing for the method for aluminium foil and positive electrode to solve conventional molecular solvent and alkali process
Problem is stated, a kind of method using ionic liquid separating waste, worn active substance of lithium ion battery anode and aluminium foil, this method are provided
Have many advantages, such as that the time is short, temperature is low, process flow is simple, easily controllable and amplification has potential using value.
In order to solve the above-mentioned technical problem, technical solution of the present invention is specific as follows:
A method of utilizing ionic liquid separating waste, worn active substance of lithium ion battery anode and aluminium foil, including following step
It is rapid:
Lithium ion battery positive plate after dismantling, sorting is put into ionic liquid by step 1, ultrasonic at normal temperature
Wave oscillation, stands；
Step 2 takes out aluminium foil, is separated by filtration ionic liquid and black solid powder；
The ionic liquid of step 2 is carried out purifying drying process by step 3, obtains the ionic liquid that can be recycled；
The black solid powder of step 2 is dried step 4, obtains can be used as extraction process Call Provision, nickel, manganese, lithium
The raw material of metallic element.
In the above-mentioned technical solutions, the ionic liquid be 1- butyl -3- methylimidazole acetate ([Bmim] [Ac]) or
1- ethyl-3-methylimidazole acetate ([Emim] [Ac]) ionic liquid.
In the above-mentioned technical solutions, the lithium ion battery positive plate is ternary battery, lithium manganate battery or cobalt
The positive plate of acid lithium battery.
In the above-mentioned technical solutions, the time of the supersonic oscillations is 5-20min.
In the above-mentioned technical solutions, the lithium ion battery positive plate and the solid-to-liquid ratio of ionic liquid are 1:5~20.
The beneficial effects of the present invention are:
Method provided by the invention using ionic liquid separating waste, worn active substance of lithium ion battery anode and aluminium foil is adopted
Positive active material and aluminium foil are separated with intensified by ultrasonic wave ionic liquid, ionic liquid is increased by the cavitation of ultrasonic wave
Penetration power, substantially increase the separative efficiency of positive active material and aluminium foil.
Method provided by the invention using ionic liquid separating waste, worn active substance of lithium ion battery anode and aluminium foil, into
One step uses 1- butyl -3- methylimidazole acetate ([Bmim] [Ac]) or 1- ethyl-3-methylimidazole acetate ([Emim]
[Ac]) ionic liquid is as solvent, and compared with the molecular solvents dissolution method such as NMP, the present invention uses green solvent [Bmim] [Ac]
[Emim] [Ac] ionic liquid have the advantages that as solvent it is not volatile equal, while such ionic liquid have low-viscosity and
Good thermal stability is easily isolated and operates with ionic liquid recovery process.
Method pair provided by the invention using ionic liquid separating waste, worn active substance of lithium ion battery anode and aluminium foil
Ionic liquid is separated by filtration, and treated, and ionic liquid can be recycled.
It is provided by the invention to have using the method for ionic liquid separating waste, worn active substance of lithium ion battery anode and aluminium foil
The advantages that having time is short, temperature is low, process flow is simple, easily controllable and amplification, has potential using value.
Detailed description of the invention
Fig. 1 is the side provided by the invention using ionic liquid separating waste, worn active substance of lithium ion battery anode and aluminium foil
The process flow chart of method.
Specific embodiment
Method provided by the invention using ionic liquid separating waste, worn active substance of lithium ion battery anode and aluminium foil is adopted
With the PVDF binder of intensified by ultrasonic wave ion liquid dissolving old and useless battery anode, the efficient of positive active material and aluminium foil is realized
Separation.It is preferred that ionic liquid used is 1- butyl -3- methylimidazole acetate ([Bmim] [Ac]) or 1- ethyl-3-methylimidazole
Acetate ([Emim] [Ac]) ionic liquid.It is preferably applied to separation of tertiary battery, lithium manganate battery or cobalt acid lithium battery
Positive plate.
Be illustrated with reference to Fig. 1 the present invention provide it is a kind of using ionic liquid separating waste, worn active substance of lithium ion battery anode with
The method of aluminium foil, the specific steps of this method are as follows:
Step 1, will dismantling, sorting after lithium ion battery positive plate be put into ionic liquid, solid-to-liquid ratio be 1:5~
20,5~20min of supersonic oscillations, stands at normal temperature；
Step 2 takes out aluminium foil, is separated by filtration the black solids powder such as ionic liquid and positive active material, conductive agent；
Step 3 carries out purifying drying process to the ionic liquid of step 2, and ionic liquid can be recycled；
After step 4, black powder are dry, the raw material of the metallic elements such as extraction process Call Provision, nickel, manganese, lithium can be used as.
Embodiment 1
Waste and old ternary battery anode slice after dismantling, sorting is put into 1- ethyl-3-methylimidazole acetate ionic liquid
In, solid-to-liquid ratio 1:5, supersonic oscillations 20min, stands at normal temperature.Aluminium foil is taken out, ionic liquid and anode are separated by filtration
The black solids powder such as active material, conductive agent can be recycled after the purified drying process of ionic liquid.Black powder is dry
Afterwards, it can be used as the raw material of the metallic elements such as extraction process Call Provision, nickel, manganese, lithium.
Embodiment 2
Waste lithium manganese oxide battery positive plate after dismantling, sorting is put into 1- butyl -3- methylimidazole acetate ion liquid
In body, solid-to-liquid ratio 1:10, supersonic oscillations 10min, is stood at normal temperature.Take out aluminium foil, be separated by filtration ionic liquid with
The black solids powder such as positive active material, conductive agent can be recycled after the purified drying process of ionic liquid.Black powder
After drying, the raw material of the metallic elements such as extraction process recycling manganese, lithium can be used as.
Embodiment 3
Waste and old cobalt acid lithium battery positive plate after dismantling, sorting is put into 1- butyl -3- methylimidazole acetate ion liquid
In body, solid-to-liquid ratio 1:20, supersonic oscillations 5min, is stood at normal temperature.Take out aluminium foil, be separated by filtration ionic liquid with just
The black solids powder such as pole active material, conductive agent can be recycled after the purified drying process of ionic liquid.Black powder is dry
After dry, the raw material of the metallic elements such as extraction process Call Provision, lithium can be used as.
Therefore the method for the invention using ionic liquid separating waste, worn active substance of lithium ion battery anode and aluminium foil, is adopted
With 1- butyl -3- methylimidazole acetate ([Bmim] [Ac]), 1- ethyl-3-methylimidazole acetate ([Emim] [Ac]) ion
Liquid dissolves Kynoar (PVDF) binder as solvent, by intensified by ultrasonic wave, realizes positive active material and aluminium foil
Efficiently separate, ionic liquid can be recycled after processing.This method have the time is short, temperature is low, process flow is simple, easily
In the control and amplification the advantages that, there is potential using value.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (5)
1. a kind of method using ionic liquid separating waste, worn active substance of lithium ion battery anode and aluminium foil, which is characterized in that
The following steps are included:
Lithium ion battery positive plate after dismantling, sorting is put into ionic liquid by step 1, and ultrasonic wave shakes at normal temperature
It swings, stands；
Step 2 takes out aluminium foil, is separated by filtration ionic liquid and black solid powder；
The ionic liquid of step 2 is carried out purifying drying process by step 3, obtains the ionic liquid that can be recycled；
The black solid powder of step 2 is dried step 4, obtains can be used as extraction process Call Provision, nickel, manganese, lithium metal
The raw material of element.
2. the side according to claim 1 using ionic liquid separating waste, worn active substance of lithium ion battery anode and aluminium foil
Method, which is characterized in that the ionic liquid is 1- butyl -3- methylimidazole acetate or 1- ethyl-3-methylimidazole acetate.
3. the side according to claim 1 using ionic liquid separating waste, worn active substance of lithium ion battery anode and aluminium foil
Method, which is characterized in that the lithium ion battery positive plate be ternary battery, lithium manganate battery or cobalt acid lithium battery just
Pole piece.
4. utilization ionic liquid separating waste, worn active substance of lithium ion battery anode according to claim 1 to 3
With the method for aluminium foil, which is characterized in that the time of the supersonic oscillations is 5-20min.
5. the side according to claim 4 using ionic liquid separating waste, worn active substance of lithium ion battery anode and aluminium foil
Method, which is characterized in that the lithium ion battery positive plate and the solid-to-liquid ratio of ionic liquid are 1:5~20.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811392957.XA CN109536713B (en) | 2018-11-21 | 2018-11-21 | Method for separating anode active material of waste lithium ion battery and aluminum foil by using ionic liquid |
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| CN201811392957.XA CN109536713B (en) | 2018-11-21 | 2018-11-21 | Method for separating anode active material of waste lithium ion battery and aluminum foil by using ionic liquid |
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Cited By (9)
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| CN109921126A (en) * | 2019-04-16 | 2019-06-21 | 常熟理工学院 | A method of active material is recycled from waste and old anode material for lithium-ion batteries containing cobalt |
| CN110331290A (en) * | 2019-07-08 | 2019-10-15 | 中南大学 | The method that liquid phase method recycles lithium and transition elements in waste lithium cell positive electrode |
| CN111139499A (en) * | 2019-12-19 | 2020-05-12 | 西安交通大学 | Lithium ion battery heavy metal recovery method based on microwave-assisted eutectic solvent |
| WO2021198600A1 (en) * | 2020-04-01 | 2021-10-07 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Method for recycling an electrode |
| CN114317984A (en) * | 2022-01-04 | 2022-04-12 | 华北理工大学 | Method for selectively soaking zinc by utilizing cyclone classification-ionic liquid-ultrasonic synergy |
| WO2022074328A1 (en) * | 2020-10-09 | 2022-04-14 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Method for opening an electrochemical generator |
| CN115149140A (en) * | 2022-08-23 | 2022-10-04 | 宜春天赐高新材料有限公司 | Method for recovering iron and lithium from waste lithium iron phosphate batteries |
| CN115889419A (en) * | 2022-10-11 | 2023-04-04 | 安徽格派锂电循环科技有限公司 | Method for effectively separating positive electrode material and aluminum foil from waste lithium battery |
| CN116742174A (en) * | 2023-04-19 | 2023-09-12 | 江苏理工学院 | Method for separating positive electrode active material of waste lithium battery from aluminum foil |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109921126B (en) * | 2019-04-16 | 2020-07-10 | 常熟理工学院 | Method for recovering active material from waste cobalt-containing lithium ion battery positive electrode material |
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| CN111139499A (en) * | 2019-12-19 | 2020-05-12 | 西安交通大学 | Lithium ion battery heavy metal recovery method based on microwave-assisted eutectic solvent |
| WO2021198600A1 (en) * | 2020-04-01 | 2021-10-07 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Method for recycling an electrode |
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| WO2022074328A1 (en) * | 2020-10-09 | 2022-04-14 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Method for opening an electrochemical generator |
| CN114317984A (en) * | 2022-01-04 | 2022-04-12 | 华北理工大学 | Method for selectively soaking zinc by utilizing cyclone classification-ionic liquid-ultrasonic synergy |
| CN115149140A (en) * | 2022-08-23 | 2022-10-04 | 宜春天赐高新材料有限公司 | Method for recovering iron and lithium from waste lithium iron phosphate batteries |
| CN115889419A (en) * | 2022-10-11 | 2023-04-04 | 安徽格派锂电循环科技有限公司 | Method for effectively separating positive electrode material and aluminum foil from waste lithium battery |
| CN116742174A (en) * | 2023-04-19 | 2023-09-12 | 江苏理工学院 | Method for separating positive electrode active material of waste lithium battery from aluminum foil |
| CN116742174B (en) * | 2023-04-19 | 2024-03-19 | 江苏理工学院 | Method for separating positive electrode active material of waste lithium battery from aluminum foil |
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