CN108400402A - A kind of separation method of waste and old lithium dynamical battery active material and collector - Google Patents
A kind of separation method of waste and old lithium dynamical battery active material and collector Download PDFInfo
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- CN108400402A CN108400402A CN201810164912.0A CN201810164912A CN108400402A CN 108400402 A CN108400402 A CN 108400402A CN 201810164912 A CN201810164912 A CN 201810164912A CN 108400402 A CN108400402 A CN 108400402A
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- CN
- China
- Prior art keywords
- active material
- collector
- solvent
- waste
- lithium dynamical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
-
- 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
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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 the separation methods for planting waste and old lithium dynamical battery active material and collector, include the following steps：(1) power battery after dismantling electric discharge, obtains electrode；(2) electrode is immersed in solvent, 3 4h of heating stirring；(3) it filters, filter residue is rinsed 35 times with detergent, it is to remove solvent, the filter residue after washing is dry at 80 100 DEG C, obtain collector；(4) filtrate is centrifuged, obtains solid sediment, the solid sediment is cleaned 56 times with deionized water, dry 4 6h at 80 120 DEG C；By the solid sediment after drying, broken, screening, obtains active material；The solvent is one or more in amide compound, sulfoxide compound and pyrrolidone-2 compounds.Solvent in the present invention is strong to the solvability of binder PVDF, and after separation collector and active material, the rate of recovery for recycling collector and active material is high.
Description
Technical field
The invention belongs to technical field of lithium batteries, and in particular to a kind of separation side of lithium battery collector and active material
Method.
Background technology
Depleted, environment the serious pollution of the fossil fuels such as global main energy sources coal, oil, natural gas is to the mankind's
Existence constitutes a serious threat, this just promotes the mankind to find clean renewable new energy.Electric energy is as economic development, scientific and technological progress
Major impetus, be widely used in the every field such as power, illumination, metallurgy, chemistry, weaving, communication, broadcast, and battery is made
For the carrier of electric energy, demand also increasingly increases severely, but the battery learies generated therewith make people startling.In China, every year
10,000,000,000 old and useless batterys are about generated, about 300,000 tons of weight, wherein electric automobile power battery add up about 120,000 tons of learies, accounts for
It is bigger；If handling power battery by the way of landfill, the water body of 4,000,000,000 m3 will be caused to be polluted, the soil of 1500km3
Earth, which is lost, uses function, is greatly threatened being generated to the ecological environment of the mankind.In waste and old lithium ion battery containing cobalt, nickel, iron,
The high value metals such as aluminium, copper, and China belongs to the more rare type country of resource, especially cobalt resource, is balanced in a manner of import
Domestic increasing need, and metallic nickel and manganese are non-renewable resources.Take certain processing method to waste and old power
Battery recycling recycles, and can reduce the pollution to environment, and realize recycling for resource, has important war to social development
Slightly meaning and economic value.
Patent CN201110314470.1 discloses a kind of method recycling valuable metal from waste lithium cell.This method is adopted
With calcining expansion thermal release method, the organic adhesives such as removal PVDF, to detach collector and active material, but this method is reacted
Condition is violent, and high energy consumption, organic efficiency is low, causes air pollution.
Patent CN201510677096.X is disclosed a kind of cooperateing with work in anionic surfactant and acidic environment
Under, the method for making collector be detached with active material by way of heating stirring realizes point of collector and active material
From and recycle.The method needs that hydrochloric acid is added in processing procedure, will produce into a certain amount of waste liquid, and can not recycle, waste liquid
It need to be handled to avoid the secondary pollution to environment, cost for wastewater treatment is high.
Invention content
It is an object of the invention to：Above-mentioned deficiency in the prior art is solved, it is small, environmentally safe to provide a kind of energy consumption
The method that is detached with active material of collector.
To achieve the goals above, the technical solution adopted by the present invention is：A kind of waste and old lithium dynamical battery active material with
The separation method of collector, includes the following steps：
(1) lithium dynamical battery after dismantling electric discharge, obtains electrode；
(2) electrode is immersed in solvent, heating stirring 3-4h；
(3) it filters, filter residue is rinsed 3-5 times with detergent, to remove solvent, the filter residue after washing is done at 80-100 DEG C
It is dry, obtain collector；
(4) filtrate is centrifuged, obtains solid sediment, the solid sediment is cleaned 5-6 times with deionized water,
Dry 4-6h at 80-120 DEG C；By the solid sediment after drying, broken, screening, obtains active material；
The solvent is one or more in amide compound, sulfoxide compound and pyrrolidone-2 compounds.
Further, a concentration of 5-10mol/L of the solvent.
Further, the detergent is distilled water or absolute ethyl alcohol or ethanol water.
Further, in the step (4), the centrifugal rotational speed in the centrifugal process is 3000 turns/min -5000
Turn/min.
Further, the aperture of the sieve used in the screening process is 800-1250 mesh.
By adopting the above-described technical solution, the beneficial effects of the invention are as follows：
1, the collector in waste and old lithium dynamical battery and the quick and complete purpose detached of active material can be achieved in the present invention, and
The integrality that current collector structure can preferably be kept conducive to secondary use, is sold outside, and the active material of recycling can be re-used for material
The synthesis of material；
2, the organic solvent that the present invention uses has the characteristics that dissolubility is strong, cheap, without side-effects to human body；
3, the method for the present invention is simple for process, easy to operate, and the rate of recovery of collector is high, while can reduce production cost, to lithium
Ion battery manufacturing industry is significant.
4, the present invention can be applied to the processing of positive and negative electrode simultaneously, be suitable for a plurality of types of collectors and active material,
And the rate of recovery is higher, regenerant reuses efficient.Compare existing treatment technology, present invention process is more simplified and at low cost
It is honest and clean, it is particularly suitable for large-scale lithium battery remanufacture.
Description of the drawings
The LiNi that Fig. 1 is obtained by the embodiment of the present invention 10.5Co0.2Mn0.3O2Scanning electron microscope (SEM) photograph schematic diagram；
The LiNi that Fig. 2 is obtained by the embodiment of the present invention 10.5Co0.2Mn0.3O2Discharge curve under different multiplying.
Specific implementation mode
With reference to attached drawing 1-2, specific description is done to embodiments of the present invention.
Embodiment 1：
(1) lithium dynamical battery after dismantling electric discharge, collects the positive electrode of lithium dynamical battery；
(2) electrode after dismantling is immersed in the dimethyl sulfoxide (DMSO) of a concentration of 7.5mol/L, is stirred under the conditions of 35 DEG C
3h, mixing speed are 800 turns/min；
(3) solution after above-mentioned heating stirring is separated by filtration, rinses filter residue 2-3 times with deionized water, removes on filter residue
Organic solvent, by the filter residue after washing under the conditions of 80 DEG C it is dry after recycle, obtain collector；
(4) after centrifuging above-mentioned filtrate under 3000 turns/min-, 5000 turns/min rotating speeds, obtaining solvent content is
The solid sediment of 30wt%；After solid sediment is rinsed 3-5 times with deionized water, dry 6h, will do under the conditions of 80 DEG C
Solid sediment after dry is crushed to 10-20 μm, and after vibrating sub-sieve, the aperture of vibrating screen is 800 mesh, obtains active material；
Above method is equally applicable to the separation of negative electrode graphite and copper foil.
Embodiment 2：
(1) lithium dynamical battery after dismantling electric discharge, collects positive electrode；
(2) positive electrode is immersed in the dimethylacetylamide of a concentration of 5mol/L, 3h is stirred under the conditions of 40 DEG C, stirred
Speed is 1200 turns/min；
(3) it is separated by filtration, rinses filter residue 2-3 times with deionized water, remove organic solvent；By the filter residue after washing at 90 DEG C
Under the conditions of it is dry after recycle, obtain collector；
(4) after centrifuging filtrate under 4000 turns/min rotating speeds, it is consolidating for 5wt%-30wt% to obtain solvent content
Body sediment；After solid sediment is rinsed 3-5 times with deionized water, the dry 4h under the conditions of 120 DEG C；By the solid after drying
Sediment is crushed to 10-20 μm, and after vibrating sub-sieve, the aperture of vibrating screen is 1000 mesh, obtains active material；
Above method is equally applicable to the separation of negative electrode graphite and copper foil.
Embodiment 3：
(1) lithium dynamical battery after dismantling electric discharge, collects positive electrode；
(2) positive electrode is immersed in the N-Methyl pyrrolidone of a concentration of 5mol/L, 3h- is stirred under the conditions of 35 DEG C
4h, mixing speed are that 800-1200 turns/min；
(3) it is separated by filtration, rinses filter residue 2-3 times with deionized water, remove organic solvent；By the filter residue after washing 100
It is recycled after drying under the conditions of DEG C, obtains collector；
(4) after centrifuging filtrate under the rotating speed of 5000 turns/min, it is heavy to obtain the solid that solvent content is 20wt%
Starch；After solid sediment is rinsed 3-5 times with deionized water, dry 4h, the solid after drying is precipitated under the conditions of 100 DEG C
Object is crushed to 10-20 μm, after vibrating sub-sieve, obtains active material；
Above method is equally applicable to the separation of negative electrode graphite and copper foil.
Embodiment 4：
A kind of separation method of waste and old lithium dynamical battery active material and collector, includes the following steps：
(1) lithium dynamical battery after dismantling electric discharge, collects positive electrode；
(2) positive electrode is immersed in the dimethylacetylamide of a concentration of 5mol/L concentration, 3h- is stirred under the conditions of 35 DEG C
4h, mixing speed are that 800-1200 turns/min；
(3) separating and filtering rinses filter residue 1-2 times with absolute ethyl alcohol, removes organic solvent；By the filter residue after washing at 90 DEG C
Under the conditions of it is dry after recycle, obtain collector；
(4) it after centrifuging filtrate under 5000 turns/min rotating speeds, obtains the solid that solvent content is 10wt% and precipitates
Object；After solid sediment is rinsed 3-5 times with deionized water, the dry 5h under the conditions of 100 DEG C；By the solid sediment after drying
It is crushed to 10-15 μm, after vibrating sub-sieve, the aperture of vibrating screen is 1250 mesh, obtains active material；
Above method is equally applicable to the separation of negative electrode graphite and copper foil.
Embodiment 5：
(1) lithium dynamical battery after dismantling electric discharge, collects positive electrode；
(2) positive electrode is immersed in two N-Methyl pyrrolidones of a concentration of 5mol/L, 4h is stirred under the conditions of 30 DEG C,
Mixing speed is 800 turns/min；
(3) liquid separation is filtered, filter residue is rinsed 2-3 times with deionized water, removes organic solvent；By the filter residue after washing 100
It is recycled after drying under the conditions of DEG C, obtains collector；
(4) it after centrifuging filtrate under 5000 turns/min rotating speeds, obtains the solid that solvent content is 5wt% and precipitates
Object；After solid sediment is rinsed 3-5 times with deionized water, the dry 4h under the conditions of 120 DEG C；By the solid sediment after drying
It is crushed to 10-15 μm, after vibrating sub-sieve, obtains active material；
Above method is equally applicable to the separation of negative electrode graphite and copper foil.
In the above embodiments 1-5, when positive electrode or negative electrode are immersed into solvent, for adhesion activity substance and
The binder PVDF dissolvings of collector in a solvent, make the collector of electrode be detached with the active material of adherency on a current collector,
Active material forms mixture with solvent, and collector does not dissolve in solvent, and collector keeps original shape in a solvent, passes through
The mode for dissolving binder, will not destroy the original shape of collector, maintain the integrality of collector, convenient for returning for collector
It is received in utilization, while will not also destroy the activity of active material.
Solvent in the present invention is strong to the solvability of binder PVDF, after separation collector and active material, recycling
The rate of recovery of collector and active material is high, and method environmental pollution of the invention is small, easy to operate, and the solvent used is cheap
The advantages that.The method of the present invention can be used in the recycling of waste and old lithium dynamical battery.
It is above the wherein specific implementation of the present invention, the description thereof is more specific and detailed, but can not therefore manage
Solution is the limitation to the scope of the claims of the present invention.It should be pointed out that for those of ordinary skill in the art, not departing from
Under the premise of present inventive concept, various modifications and improvements can be made, these obvious alternative forms belong to this hair
Bright protection domain.
Claims (5)
1. a kind of separation method of waste and old lithium dynamical battery active material and collector, includes the following steps：
(1) lithium dynamical battery after dismantling electric discharge, obtains electrode；
(2) electrode is immersed in solvent, heating stirring 3-4h；
(3) it filters, filter residue is rinsed 3-5 times with detergent, it is to remove solvent, the filter residue after washing is dry at 80-100 DEG C,
Obtain collector；
(4) filtrate is centrifuged, obtains solid sediment, the solid sediment is cleaned 5-6 times with deionized water, in 80-120
Dry 4-6h at DEG C；By the solid sediment after drying, broken, screening, obtains active material；
The solvent is one or more in amide compound, sulfoxide compound and pyrrolidone-2 compounds.
2. the separation method of waste and old lithium dynamical battery active material and collector according to claim 1, it is characterised in that：
A concentration of 5-10mol/L of the solvent.
3. the separation method of waste and old lithium dynamical battery active material and collector according to claim 1, it is characterised in that：
The detergent is distilled water or absolute ethyl alcohol or ethanol water.
4. the separation method of waste and old lithium dynamical battery active material and collector according to claim 1, it is characterised in that：
In the step (4), the centrifugal rotational speed in the centrifugal process is 3000 turns/min-, 5000 turns/min.
5. the separation method of waste and old lithium dynamical battery active material and collector according to claim 1, it is characterised in that：
The aperture of the sieve used in the screening process is 800-1250 mesh.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810164912.0A CN108400402A (en) | 2018-02-27 | 2018-02-27 | A kind of separation method of waste and old lithium dynamical battery active material and collector |
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| CN201810164912.0A CN108400402A (en) | 2018-02-27 | 2018-02-27 | A kind of separation method of waste and old lithium dynamical battery active material and collector |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111540974A (en) * | 2020-05-26 | 2020-08-14 | 四川省有色冶金研究院有限公司 | Method for recycling lithium ion battery anode material |
| CN112207119A (en) * | 2020-10-10 | 2021-01-12 | 荆门市格林美新材料有限公司 | Method for treating battery black powder |
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| CN1953269A (en) * | 2006-11-01 | 2007-04-25 | 浙江工业大学 | A recovery method for waste lithium ion cell |
| CN101192693A (en) * | 2006-11-30 | 2008-06-04 | 比亚迪股份有限公司 | Recovery method for active matter from waste material containing lithium ionic cell anode active matter |
| CN105489960A (en) * | 2015-10-20 | 2016-04-13 | 李佳坤 | Separation method for current collector and active material of lithium battery and application of separation method |
| CN105576314A (en) * | 2015-12-18 | 2016-05-11 | 山东精工电子科技有限公司 | Recycling method of positive electrode piece of lithium ion battery |
-
2018
- 2018-02-27 CN CN201810164912.0A patent/CN108400402A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1953269A (en) * | 2006-11-01 | 2007-04-25 | 浙江工业大学 | A recovery method for waste lithium ion cell |
| CN101192693A (en) * | 2006-11-30 | 2008-06-04 | 比亚迪股份有限公司 | Recovery method for active matter from waste material containing lithium ionic cell anode active matter |
| CN105489960A (en) * | 2015-10-20 | 2016-04-13 | 李佳坤 | Separation method for current collector and active material of lithium battery and application of separation method |
| CN105576314A (en) * | 2015-12-18 | 2016-05-11 | 山东精工电子科技有限公司 | Recycling method of positive electrode piece of lithium ion battery |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111540974A (en) * | 2020-05-26 | 2020-08-14 | 四川省有色冶金研究院有限公司 | Method for recycling lithium ion battery anode material |
| CN111540974B (en) * | 2020-05-26 | 2021-11-09 | 四川省有色冶金研究院有限公司 | Method for recycling lithium ion battery anode material |
| CN112207119A (en) * | 2020-10-10 | 2021-01-12 | 荆门市格林美新材料有限公司 | Method for treating battery black powder |
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Application publication date: 20180814 |