CN105304966B - A kind of environmental protection recycling method of lithium ion battery - Google Patents
A kind of environmental protection recycling method of lithium ion battery Download PDFInfo
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- CN105304966B CN105304966B CN201410267043.6A CN201410267043A CN105304966B CN 105304966 B CN105304966 B CN 105304966B CN 201410267043 A CN201410267043 A CN 201410267043A CN 105304966 B CN105304966 B CN 105304966B
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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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Abstract
The invention discloses a kind of environmental protection recycling methods of lithium ion battery; the method is that the core of lithium ion cell after removing the shell of lithium ion battery is put into high-temp liquid; diaphragm therein is set to be decomposed into gas and/or oil discharge by the heat effect of high-temp liquid; separate positive electrode from the plus plate current-collecting body of anode, negative electrode material is separated from the negative current collector of cathode；Then high-temp liquid is soluble in water, the mixture filter cake of plus plate current-collecting body, negative current collector, positive electrode and negative electrode material is obtained by filtration；Mixture filter cake is further separated, positive electrode, plus plate current-collecting body and negative current collector can be respectively obtained.The method of the present invention has many advantages, such as separative efficiency height, simple process, environmental protection, at low cost, can solve the problems, such as the pollution and recycling of waste lithium ion.
Description
Technical field
The present invention relates to a kind of recovery methods of battery, are to be related to a kind of environmentally friendly recycling side of lithium ion battery specifically
Method.
Background technique
Now due to scrapping for electronic product is more and more, the learies of the lithium ion battery for electronic product are also more next
Bigger, how environmental protection recycling lithium ion battery is also more and more important.It is returned about the correlation of lithium ion battery in the prior art
Receipts technology, such as: Chinese patent application CN01130735.8, entitled " method of metal is recycled from used Li ion cell "
Invention in disclose a kind of recovery method, although the invention can also achieve the purpose that recycling wherein metal, in removal process
In use high temperature furnace and roast, and additionally use the means that sour corrosion is added, not only create new environment in removal process
Pollution, and at high cost, complex process are not suitable for scale recycling and require！Therefore, a kind of high-efficient, pollution-free, cost is researched and developed
The low environmental protection recycling method about lithium ion battery will have the pollution and recycling that solve the problems, such as waste lithium ion
Important value and social effect.
Summary of the invention
It is an object of the invention to overcome the deficiencies of existing technologies, a kind of separative efficiency height, simple process are provided, without dirt
The environmental protection recycling method of dye, lithium ion battery at low cost.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of environmental protection recycling method of lithium ion battery, the lithium ion battery include casing of lithium ion battery and lithium ion
Battery, the core of lithium ion cell include the positive electrode, the negative electrode and the separator, and the anode includes positive electrode and anode collection
Body, the cathode include negative electrode material and negative current collector；The method be lithium after removing the shell of lithium ion battery from
Sub- battery is put into high-temp liquid, so that diaphragm therein is decomposed into gas and/or oil row by the heat effect of high-temp liquid
Out, and by the heat effect of high-temp liquid it separates positive electrode from the plus plate current-collecting body of anode, makes negative electrode material
It is separated from the negative current collector of cathode；Then it will contain plus plate current-collecting body, positive electrode, negative current collector and cathode material
The high-temp liquid of material is soluble in water, and the mixing of plus plate current-collecting body and negative current collector and positive electrode and negative electrode material is obtained by filtration
Object filter cake, or the mixture filter cake and positive electrode and negative electrode material and high temperature of plus plate current-collecting body and negative current collector is obtained by filtration
The mixed filtrate of liquid；The temperature of the high-temp liquid is not less than the decomposition temperature of diaphragm.
The environmental protection recycling method of lithium ion battery of the present invention also has following improvement:
1, the recyclable device of gas and/or oil is provided with above the container for holding high-temp liquid.
2, separation net is provided in the container for holding high-temp liquid.
3, when plus plate current-collecting body is aluminium foil, negative pole currect collecting is copper foil, the fusing point of the temperature of the high-temp liquid between aluminium
Between the fusing point of copper.
4, the heating of high-temp liquid substep is carried out, its temperature is made to reach diaphragm decomposition temperature between 450 degree first；To
Diaphragm is warming up between the fusing point of aluminium and the fusing point of copper again after decomposing completely.
5, the high-temp liquid is fuse salt.
6, do not occur between the high-temp liquid and plus plate current-collecting body, positive electrode, negative current collector and negative electrode material
Chemical reaction.
7, secondary filter is carried out to the mixed filtrate for the positive electrode and negative electrode material and high-temp liquid being obtained by filtration, made just
Pole material and negative electrode material are isolated from mixed filtrate.
8, when the mixture of obtained plus plate current-collecting body and negative current collector is the mixture of copper and aluminium, using between the two
Different melting points or difference of specific gravity carry out separating treatment.
9, when the mixture of the positive electrode and negative electrode material isolated is the mixture of lithium salts and graphite powder, by adding
Heat makes graphite powder that voloxidation occur with isolated lithium salts.
Compared with prior art, the invention has the following beneficial effects:
1, environmentally friendly: in removal process, to be generated without waste water, exhaust gas and waste residue.
2, recycling: plus plate current-collecting body therein, negative current collector, positive electrode, diaphragm are all recycled.
3, at low cost: due to not being added and consuming any chemicals in entire removal process, cost recovery is low.
Detailed description of the invention
Fig. 1 is the process flow chart that a kind of pair of lithium ion battery that embodiment 1 provides carries out environmentally friendly recycling.
Fig. 2 is another process flow chart that environmentally friendly recycling is carried out to lithium ion battery that embodiment 2 provides.
Specific embodiment
Technical solution of the present invention is further elaborated below with reference to embodiment and attached drawing:
A kind of environmental protection recycling method of lithium ion battery provided by the invention, includes the following steps:
Core of lithium ion cell after the shell of lithium ion battery is removed is put into high-temp liquid, and high-temp liquid is passed through
Heat effect make diaphragm therein be decomposed into gas and/or oil discharge, and by the heat effect of high-temp liquid make positive electrode from
It is separated on the plus plate current-collecting body of anode, separates negative electrode material from the negative current collector of cathode；Then will contain
Plus plate current-collecting body, positive electrode, the high-temp liquid of negative current collector and negative electrode material are soluble in water, and plus plate current-collecting body is obtained by filtration
With the mixture filter cake of negative current collector and positive electrode and negative electrode material, or plus plate current-collecting body and negative current collector is obtained by filtration
Mixture filter cake and positive electrode and negative electrode material and high-temp liquid mixed filtrate；The temperature of the high-temp liquid is not less than
The decomposition temperature of diaphragm.
When the mixture of positive electrode, plus plate current-collecting body, negative electrode material and negative current collector is obtained by filtration, to mixture
After carrying out cleaning, drying processing, due to positive electrode and negative electrode material in powdery and plus plate current-collecting body and negative current collector are in particle
Or it is blocky, thus can be by adjusting the mesh size of sieve, using method for sieving by positive electrode and negative electrode material and anode
Collector and negative current collector separation, obtain the mixture and plus plate current-collecting body and negative pole currect collecting containing positive electrode and negative electrode material
The mixture of body.It can certainly otherwise, such as: being separated using difference of specific gravity using the methods of selection by winnowing.
When the mixture filter cake and positive electrode and negative electrode material and height that plus plate current-collecting body and negative current collector is obtained by filtration
When the mixed filtrate of geothermal liquid, secondary filter can be carried out, isolates positive electrode and negative electrode material from mixed filtrate, then right
The positive electrode being obtained by filtration and the mixture filter cake of negative electrode material carry out cleaning, drying processing to get positive electrode and cathode is arrived
The mixture of material；Recycling high-temp liquid is evaporated to the filtrate containing high-temp liquid.
The environmental protection recycling method of lithium ion battery of the present invention also has following improvement:
1, the recyclable device of gas and/or oil is provided with above the container for holding high-temp liquid, it can be with by recyclable device
It prevents from decomposing the gas generated and/or oil is drained into air and causes air pollution, while can also recycle, formation environmental protection,
Resource utilization.
2, when plus plate current-collecting body is aluminium foil, negative current collector is copper foil, the temperature of the high-temp liquid is between the molten of aluminium
Between point and the fusing point of copper.When the temperature of the high-temp liquid is higher than the fusing point of aluminium, aluminium foil will be fused into graininess aluminium, hold
Easily separated with copper foil.
3, be provided with separation net in the container for holding high-temp liquid, separation net can allow cobalt acid lithium powder and graininess aluminium from
In leak down, and copper foil is stopped；When separation net is taken out from high-temp liquid, so that it may realize the separation of copper.
4, the heating of high-temp liquid substep is carried out, its temperature is made to reach diaphragm decomposition temperature between 450 degree first；To
Diaphragm is warming up between the fusing point of aluminium and the fusing point of copper again after decomposing completely.Diaphragm can be improved using step heating and resolve into oil
Ratio, improve economic value.
5, the high-temp liquid is fuse salt.Because fuse salt can be at low cost with high temperature resistant.Such as when high-temp liquid is chlorination
Salt, such as: when the mixture of sodium chloride and/or potassium chloride, having the advantages that at low cost, easy recycling.
6, do not occur between the high-temp liquid and positive electrode, plus plate current-collecting body, negative electrode material and negative current collector
Chemical reaction.Present plus plate current-collecting body generallys use aluminium foil, negative current collector using copper foil, in case of chemical reaction copper foil
Mantoquita will be generated, and mantoquita is converted to metallic copper and will increase cost recovery.And aluminium foil will become in case of chemical reaction
At the aluminium salt of not economic value, discharge also pollutes the environment.If with high-temp liquid chemistry occurs for positive electrode such as cobalt acid lithium
Reaction cannot directly obtain cobalt acid lithium, so that its economic value can be reduced.
7, when the mixture of obtained plus plate current-collecting body and negative current collector is the mixture of copper and aluminium, using the two
Between different melting points or difference of specific gravity carry out separating treatment.Such as: being separated using the difference of specific gravity of the two by technique of preparing；
Or, using the two different melting points by aluminium melt and copper still maintains solid state and separates.
8, when the positive electrode and negative electrode material isolated are the mixture of lithium salts and graphite powder, stone can be made by heating
Voloxidation occurs for ink powder with isolated lithium salts.Because cobalt acid lithium still maintains stable at 900 DEG C, and at the same temperature
Graphite powder has been carbonized, and becomes carbon dioxide gas volatilization.It certainly, can be more preferable if oxygen effect is added.
Embodiment 1
Referring to Fig.1, the process flow of the environmentally friendly recycling of a kind of pair of lithium ion battery progress provided in this embodiment is as follows: will tear open
The solution obtained core of lithium ion cell of waste and old lithium ion battery is put into high-temp liquid, and the temperature general control of high-temp liquid exists
Between 400 DEG C~450 DEG C；Since the two sides of diaphragm is stained with positive and negative electrode material respectively, when diaphragm is added in high-temp liquid
When, by the heat effect of high-temp liquid, diaphragm has resolved into gas and/or oil is recycled.Continue to increase high-temp liquid
Temperature, the fusing point for making temperature be higher than aluminium make anode therein by the further heat effect of high-temp liquid lower than the fusing point of copper
Current collector aluminum foil fusing, the positive electrode lithium salts such as cobalt acid lithium being adhered to above plus plate current-collecting body will be detached from plus plate current-collecting body aluminium
Foil enters in high-temp liquid, while the graphite powder being adhered on negative current collector copper foil is also detached from enters under the action of high temperature
In high-temp liquid.Water is added in high-temp liquid, aqueous solution is formed by the dissolution of water, is once filtered, due to positive and negative electrode
Material is fine-powdered and positive and negative electrode collector is graininess and sheet, by adjusting the filter opening size of filter screen, allows fine-powdered
Positive and negative electrode material can not be passed through by strainer positive and negative electrode collector, obtain filter cake and filtrate, and obtained filter cake is particle
The positive and negative electrode collector of shape and sheet.Secondary filter is carried out to gained filtrate, obtains filter cake and the filtrate of the material containing positive and negative electrode,
Recycling high-temp liquid is evaporated to gained filtrate, to be recycled；Cleaning, drying is carried out to the filter cake of the material containing positive and negative electrode,
Obtain positive and negative electrode material blends；Heated oxide processing is carried out to gained positive and negative electrode material blends, makes graphite powder therein
It is oxidized to carbon dioxide volatilization, i.e., isolated cobalt acid lithium powder.The filter cake of the collector containing positive and negative electrode is subjected to cleaning, drying, is obtained
To positive and negative electrode collector mixture, physical separation is carried out to gained positive and negative electrode collector mixture, as utilized between the two
The different melting points of difference of specific gravity or both respectively obtain metal aluminum blocks and metal copper foil.
Embodiment 2
Referring to Fig. 2, the process flow that a kind of pair of lithium ion battery provided in this embodiment carries out environmentally friendly recycling is as follows: will tear open
The solution obtained core of lithium ion cell of waste and old lithium ion battery is put into high-temp liquid, since the two sides of diaphragm is stained with respectively
Positive and negative electrode material, when diaphragm is added in high-temp liquid, the temperature general control of high-temp liquid between 400 DEG C -450 DEG C,
The rate of recovery highest of obtained oil, is resolved by the heat effect diaphragm of high-temp liquid after diaphragm decomposes at these temperatures
Gas and/or oil are recycled.The temperature for continuing raising high-temp liquid, the fusing point for making the temperature of high-temp liquid be higher than aluminium are lower than
The fusing point of copper.By the further heat effect of high-temp liquid, plus plate current-collecting body aluminium foil therein is melted, positive collection is adhered to
Positive electrode lithium salts such as cobalt acid lithium above fluid will be detached from plus plate current-collecting body aluminium foil and enter in high-temp liquid, adhere to simultaneously
It is also detached from and enters in high-temp liquid under the action of high temperature in the graphite powder on negative current collector copper foil.It is added in high-temp liquid
Water forms aqueous solution by the dissolution of water, and filtering obtains filter cake and filtrate, is evaporated recycling high-temp liquid to gained filtrate,
To be recycled.Cleaning, drying is carried out to gained filter cake, is then sieved, since positive and negative electrode material is fine-powdered, and just,
Negative current collector is graininess and sheet, can separate the two by way of screening, fine powder is respectively obtained after screening
The positive and negative electrode material blends and graininess of shape and the positive and negative electrode collector of sheet.Positive and negative electrode material blends are carried out again
Heated oxide processing makes graphite powder therein be oxidized to carbon dioxide volatilization, isolated cobalt acid lithium powder.To positive and negative electrode afflux
Body mixture carries out physical separation, such as utilizes the different melting points of difference of specific gravity between the two or both, the two is separated,
Respectively obtain metal aluminum blocks and metal copper foil.
Be it is necessary to described herein finally: above embodiments are served only for making technical solution of the present invention further detailed
Ground explanation, should not be understood as limiting the scope of the invention, those skilled in the art's above content according to the present invention
The some nonessential modifications and adaptations made all belong to the scope of protection of the present invention.
Claims (8)
1. a kind of environmental protection recycling method of lithium ion battery, the lithium ion battery include casing of lithium ion battery and lithium-ion electric
Chi Xin, the core of lithium ion cell include the positive electrode, the negative electrode and the separator, and the anode includes positive electrode and plus plate current-collecting body,
The cathode includes negative electrode material and negative current collector；It is characterized in that: the method is after removing the shell of lithium ion battery
Core of lithium ion cell be put into high-temp liquid, by the heat effect of high-temp liquid make diaphragm therein be decomposed into gas and/
Or oil discharge, and positive electrode is separated from the plus plate current-collecting body of anode by the heat effect of high-temp liquid, make to bear
Pole material is separated from the negative current collector of cathode；Then will containing plus plate current-collecting body, positive electrode, negative current collector and
The high-temp liquid of negative electrode material is soluble in water, and plus plate current-collecting body and negative current collector and positive electrode and negative electrode material is obtained by filtration
Mixture filter cake, or the mixture filter cake and positive electrode and negative electrode material of plus plate current-collecting body and negative current collector is obtained by filtration
With the mixed filtrate of high-temp liquid；The temperature of the high-temp liquid is not less than the decomposition temperature of diaphragm, also, works as plus plate current-collecting body
When for aluminium foil, negative pole currect collecting being copper foil, the temperature of the high-temp liquid is between the fusing point of aluminium and the fusing point of copper, to high-temperature liquid
The heating substep of body carries out, and so that its temperature is reached diaphragm decomposition temperature between 450 degree first, rises again after diaphragm decomposes completely
Temperature to aluminium fusing point and copper fusing point between.
2. environmental protection recycling method according to claim 1, it is characterized in that: being provided with above the container for holding high-temp liquid
The recyclable device of gas and/or oil.
3. environmental protection recycling method according to claim 1 or 2, it is characterized in that: being arranged in the container for holding high-temp liquid
There is separation net.
4. environmental protection recycling method according to claim 1, it is characterized in that: the high-temp liquid is fuse salt.
5. environmental protection recycling method according to claim 1 or 4, it is characterized in that: the high-temp liquid and plus plate current-collecting body, just
It is not chemically reacted between pole material, negative current collector and negative electrode material.
6. environmental protection recycling method according to claim 1, it is characterized in that: when obtained plus plate current-collecting body and negative current collector
Mixture when being the mixture of copper and aluminium, using between the two different melting points or difference of specific gravity carry out separating treatment.
7. environmental protection recycling method according to claim 1, it is characterized in that: to the positive electrode and negative electrode material that are obtained by filtration
Secondary filter is carried out with the mixed filtrate of high-temp liquid, isolates positive electrode and negative electrode material from mixed filtrate.
8. environmental protection recycling method according to claim 1 or claim 7, it is characterized in that: when the positive electrode and cathode material isolated
When the mixture of material is the mixture of lithium salts and graphite powder, make graphite powder that voloxidation occur with isolated lithium by heating
Salt.
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| CN201410267043.6A CN105304966B (en) | 2014-06-16 | 2014-06-16 | A kind of environmental protection recycling method of lithium ion battery |
| PCT/CN2015/081421 WO2015192743A1 (en) | 2014-06-16 | 2015-06-15 | Resource reclamation and environmental protection method for recycling lithium ion battery wastes |
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| CN201410267043.6A CN105304966B (en) | 2014-06-16 | 2014-06-16 | A kind of environmental protection recycling method of lithium ion battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11851728B2 (en) | 2019-07-17 | 2023-12-26 | Eco-Research | Method for the treatment of accumulators, batteries and the like |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106159367B (en) * | 2016-08-11 | 2018-08-03 | 天齐锂业股份有限公司 | The recovery method of lithium metal battery negative plate |
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| US5085738A (en) * | 1989-04-24 | 1992-02-04 | Harris Windel L | Method and apparatus for thermal conversion of organic matter |
| CN101942108A (en) * | 2009-07-09 | 2011-01-12 | 巫协森 | Method for recovering base materials in classification by thermally cracking organic polymer mixtures and device thereof |
| CN103311600A (en) * | 2013-05-16 | 2013-09-18 | 清华大学 | Method and device for recycling metal in waste lithium ion batteries by water-soluble ionic liquid |
| JP2014055312A (en) * | 2012-09-11 | 2014-03-27 | Hitachi Ltd | Method for recycling lithium ion battery, and apparatus therefor |
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| US4058396A (en) * | 1976-11-26 | 1977-11-15 | Electric Power Research Institute, Inc. | Recovery of lead from batteries |
| US5085738A (en) * | 1989-04-24 | 1992-02-04 | Harris Windel L | Method and apparatus for thermal conversion of organic matter |
| CN101942108A (en) * | 2009-07-09 | 2011-01-12 | 巫协森 | Method for recovering base materials in classification by thermally cracking organic polymer mixtures and device thereof |
| JP2014055312A (en) * | 2012-09-11 | 2014-03-27 | Hitachi Ltd | Method for recycling lithium ion battery, and apparatus therefor |
| CN103311600A (en) * | 2013-05-16 | 2013-09-18 | 清华大学 | Method and device for recycling metal in waste lithium ion batteries by water-soluble ionic liquid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US11851728B2 (en) | 2019-07-17 | 2023-12-26 | Eco-Research | Method for the treatment of accumulators, batteries and the like |
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