CN108365287A - A kind of cathode of lithium battery collector short distance recovery method based on supercritical fluid - Google Patents
A kind of cathode of lithium battery collector short distance recovery method based on supercritical fluid Download PDFInfo
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- CN108365287A CN108365287A CN201810057140.0A CN201810057140A CN108365287A CN 108365287 A CN108365287 A CN 108365287A CN 201810057140 A CN201810057140 A CN 201810057140A CN 108365287 A CN108365287 A CN 108365287A
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- supercritical fluid
- lithium battery
- cathode
- short distance
- recovery method
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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
- 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
A kind of cathode of lithium battery collector short distance recovery method based on supercritical fluid, including lithium cell cathode material is put into reaction kettle, solvent, which is added, makes lithium cell cathode material be totally submerged, mechanical agitation assists, using the organic component in supercritical fluid dissolving stripping negative material under certain temperature and pressure, copper foil current collector and conductive black are detached, to recycle copper foil current collector.The present invention removes negative current collector without using organic solvent and lye, and the total removal rate of other substances of the negative materials such as electric carbon black is 94.68%；Treatment effeciency is high, and at low cost, processing procedure not will produce secondary pollution, be a kind of environmentally protective processing procedure.
Description
Technical field
The invention belongs to old and useless battery recovery technology fields, and in particular to a kind of cathode of lithium battery based on supercritical fluid
Collector short distance recovery method.
Background technology
Since lithium ion battery enters commercialization since the last century 90's, since it is high with voltage, energy is close
The advantages that degree is big, have extended cycle life, have a safety feature, memory-less effect, increasingly replaces other kinds secondary cell.Lithium battery
Negative material by 90% conductive black, 5% acetylene black, 5% binder uniformly mix, be coated in copper foil current collector.
The recovery method of existing cathode of lithium battery collector is generally handled using WATER-WASHING METHOD or high temperature method, by collector
Other are detached with conductive black etc., then directly recycle collector.As the Chinese patent literature of Publication No. CN102569941 carries
Go out a kind of method of hydrometallurgic recovery lithium ion battery material, carbon copper foil will be covered and be put into the temperature control washing pool with agitating device,
It persistently maintains water temperature between 70~100 DEG C and stirs.This method is although simple for process, but cannot wash carbon dust completely and fall.
For another example the Chinese patent literature of Publication No. CN105552468 proposes a kind of side of high temperature method processing lithium cell cathode material
The negative material of dipping pretreatment is calcined 4 hours in air atmosphere under 300~500 DEG C of hot conditions, makes negative electrode active by method
Substance is detached with copper foil.This high-temperature processing method high energy consumption, and will produce exhaust gas in processing procedure.
Therefore, it is necessary to provide a kind of simple for process, at low cost, environmental-friendly, and it can ensure that negative current collector height returns
The recovery method of yield.
Invention content
To solve the disagreeableness defect of cathode of lithium battery collector short distance removal process environment of the existing technology, this hair
It is bright that a kind of cathode of lithium battery collector short distance recovery method and reactor based on supercritical fluid are provided.
A kind of cathode of lithium battery collector short distance recovery method based on supercritical fluid, innovative point are：The side
Method is to be dissolved the organic component in lithium cell cathode material using supercritical fluid under certain temperature and pressure, to reach
Remove the purpose of negative current collector.
Further, the method is specifically after being substantially discharged lithium battery, to disassemble battery by hand, sort out cathode material
Material, and it is crushed to 4~10cm2It after size, is put into reaction kettle, solvent, which is added, makes lithium cell cathode material be totally submerged, machinery
Stirring auxiliary, is then squeezed into supercritical fluid in reaction kettle by high-pressure pump, under the conditions of certain temperature and pressure, dissolving
Adhesive in nickel-cobalt-manganese ternary lithium ion battery negative material removes negative current collector, and the negative current collector of stripping can be direct
It recycles, negative electrode active material further recycles after can leaching.
Further, the lithium cell cathode material is cobalt acid lithium battery, lithium manganate battery, ferric phosphate lithium cell, nickel cobalt
At least one of manganese ternary lithium battery, nickel cobalt aluminium ternary lithium cell cathode material.
Further, churned mechanically speed is 10~500rpm, the solid-to-liquid ratio of negative material and water is 0.1%~
10%；Preferably, mixing speed is 300~400rpm, and the solid-to-liquid ratio of negative material and water is 2%~5%.
Further, the temperature of the stripping process is 40~90 DEG C, and stripping pressure is 8~16MPa；Preferably, it removes
The temperature of process is 50~70 DEG C, and stripping pressure is 10~12MPa.
Further, the splitting time is 10~300min；Preferably, splitting time is 20~60min.
Further, the supercritical fluid is carbon dioxide, and the solvent is arbitrary in water, ethyl alcohol or acetone
It is a kind of.
A kind of reactor of the cathode of lithium battery collector short distance recycling based on supercritical fluid, including pass through piping connection
Reaction kettle and carbon dioxide storage tank, the reaction kettle outside be provided with heating mantle, be provided with blender in reaction kettle.
The first shut-off valve, the first decompression are disposed on the connecting line of further reaction kettle and carbon dioxide storage tank
Table, cooler, high-pressure pump, the second shut-off valve, the second decompression table.
The present invention proposes a kind of method of supercritical fluid short distance recycling cathode of lithium battery collector, with prior art phase
Than having the following advantages that：
The present invention removes negative current collector without using organic solvent and lye, using supercritical fluid, in certain temperature and
Copper foil current collector and conductive black are isolated under pressure, to recycle copper foil current collector, other substances of the negative materials such as electric carbon black
Total removal rate be 94.68%；Treatment effeciency is high, and at low cost, processing procedure not will produce secondary pollution, is a kind of environmentally protective
Processing procedure.
Description of the drawings
Fig. 1：The treatment with supercritical fluid system of the method for supercritical fluid short distance recycling cathode of lithium battery collector of the present invention
System structural schematic diagram.In figure：1, carbon dioxide storage tank；2, the first shut-off valve；3, the first decompression table；4, cooler；5, high-pressure pump；
6, the second shut-off valve；7, the second decompression table；8, blender；9, third shut-off valve；10, reaction kettle；11, heating mantle.
Specific implementation mode
A kind of reactor of the cathode of lithium battery collector short distance recycling based on supercritical fluid, including pass through piping connection
Reaction kettle 10 and carbon dioxide storage tank 1, reaction kettle 10 outside be provided with heating mantle 11, blender 8 is provided in reaction kettle 10.Instead
It answers and is disposed with the first shut-off valve 2, the first decompression table 3, cooler 4, height on the connecting line of kettle 10 and carbon dioxide storage tank 1
Press pump 5, the second shut-off valve 6, the second decompression table 7, reaction kettle 10 are provided with third shut-off valve 9 outside.
Embodiment 1
After cobalt acid lithium battery is substantially discharged, battery is disassembled by hand, sorts out negative material, and be crushed to 4cm2Size
Afterwards, it is put into the reaction kettle of reactor, is the 2% suitable water of addition according to solid-to-liquid ratio, and control machinery mixing speed is
Then 300rpm is squeezed into supercritical fluid in reaction kettle by high-pressure pump, the temperature for controlling stripping process is 50 DEG C, stripping pressure
Power is 10MPa, splitting time 20min, dissolves the organic component in negative material, removes negative current collector.Conductive black etc.
The total removal rate of other substances of negative material is 99.42%.
Embodiment 2
After ferric phosphate lithium cell is substantially discharged, battery is disassembled by hand, sorts out negative material, and be crushed to 7cm2Size
Afterwards, it is put into the reaction kettle of reactor, is the 4% suitable ethyl alcohol of addition according to solid-to-liquid ratio, and control machinery mixing speed is
Then 400rpm is squeezed into supercritical fluid in reaction kettle by high-pressure pump, the temperature for controlling stripping process is 60 DEG C, stripping pressure
Power is 11MPa, splitting time 40min, dissolves the organic component in negative material, removes negative current collector.Conductive black etc.
The total removal rate of other substances of negative material is 98.73%.
Embodiment 3
After nickel-cobalt-manganese ternary lithium battery is substantially discharged, battery is disassembled by hand, sorts out negative material, and be crushed to
10cm2It after size, is put into the reaction kettle of reactor, is the 5% suitable water of addition according to solid-to-liquid ratio, and control machinery stirring is fast
Degree is 500rpm, then squeezes into supercritical fluid in reaction kettle by high-pressure pump, and the temperature for controlling stripping process is 60 DEG C, stripping
Tripping power is 12MPa, splitting time 90min, dissolves the organic component in negative material, removes negative current collector.Electric carbon black
The total removal rate of other substances of equal negative materials is 99.10%.
Embodiment 4
After lithium manganate battery is substantially discharged, battery is disassembled by hand, sorts out negative material, and be crushed to 1cm2Size
Afterwards, it is put into the reaction kettle of reactor, is the 10% suitable water of addition according to solid-to-liquid ratio, and control machinery mixing speed is
Then 10rpm is squeezed into supercritical fluid in reaction kettle by high-pressure pump, the temperature for controlling stripping process is 40 DEG C, stripping pressure
Power is 8MPa, splitting time 300min, dissolves the organic component in negative material, removes negative current collector.Electric carbon black etc. is negative
The total removal rate of other substances of pole material is 90.25%.
Embodiment 5
Nickel-cobalt-manganese ternary lithium battery and nickel cobalt aluminium ternary lithium battery are pressed 1:After 1 mixing is substantially discharged, battery is disassembled by hand,
Negative material is sorted out, according to 1:1 mixes and is crushed to 5cm2It after size, is put into the reaction kettle of reactor, according to solid-to-liquid ratio
Suitable water is added for 0.1%, and control machinery mixing speed is 420rpm, then squeezes into supercritical fluid by high-pressure pump
In reaction kettle, the temperature for controlling stripping process is 90 DEG C, and stripping pressure is 12MPa, splitting time 20min, and dissolving battery is negative
Organic component in the material of pole removes negative current collector.The total removal rate of other substances of the negative materials such as electric carbon black is
94.68%.
The technological parameter and stripping rate result after corresponding lift-off processing that following table is example 1-5
As seen from the above table, peeling effect of the present invention is good, simple for process, at low cost, and the stripping rate of negative current collector exists
90% or more, processing not will produce secondary pollution, be a kind of environmentally friendly green processing procedure.
Claims (10)
1. a kind of cathode of lithium battery collector short distance recovery method based on supercritical fluid, which is characterized in that including lithium is electric
Pond negative material is put into reaction kettle, and solvent, which is added, makes lithium cell cathode material be totally submerged, mechanical agitation auxiliary, in a constant temperature
Using the organic component in supercritical fluid dissolving stripping negative material under degree and pressure.
2. the cathode of lithium battery collector short distance recovery method based on supercritical fluid, feature exist as described in claim 1
In the lithium cell cathode material is after being substantially discharged lithium battery, to disassemble battery by hand, sort out negative material, and break
It is broken to 4~10cm2Size；The supercritical fluid is squeezed by high-pressure pump in reaction kettle.
3. the cathode of lithium battery collector short distance recovery method based on supercritical fluid as claimed in claim 1 or 2, feature
Be, the lithium cell cathode material be cobalt acid lithium battery, lithium manganate battery, ferric phosphate lithium cell, nickel-cobalt-manganese ternary lithium battery,
At least one of nickel cobalt aluminium ternary lithium battery nickel-cobalt-manganese ternary lithium cell cathode material.
4. the cathode of lithium battery collector short distance recovery method based on supercritical fluid, feature exist as described in claim 1
It is 10~500rpm in, churned mechanically speed, the solid-to-liquid ratio of negative material and water is 0.1%~10%.
5. the cathode of lithium battery collector short distance recovery method based on supercritical fluid, feature exist as claimed in claim 4
It is 300~400rpm in, churned mechanically speed, the solid-to-liquid ratio of negative material and water is 2%~5%.
6. the cathode of lithium battery collector short distance recovery method based on supercritical fluid, feature exist as described in claim 1
In the temperature of, supercritical fluid dissolving stripping negative material is 40~90 DEG C, pressure is 8~16MPa, splitting time is 10~
300min。
7. the cathode of lithium battery collector short distance recovery method based on supercritical fluid, feature exist as claimed in claim 6
In the temperature of, supercritical fluid dissolving stripping negative material is 50~70 DEG C, pressure is 10~12MPa, splitting time is 20~
60min。
8. the cathode of lithium battery collector short distance recovery method based on supercritical fluid, feature exist as described in claim 1
In the supercritical fluid is carbon dioxide, and the solvent is any one in water, ethyl alcohol or acetone.
9. a kind of reactor of the cathode of lithium battery collector short distance recycling based on supercritical fluid, which is characterized in that including logical
It crosses outside the reaction kettle and carbon dioxide storage tank, the reaction kettle of piping connection and is provided with heating mantle, stirring is provided in reaction kettle
Device.
10. the reactor of the cathode of lithium battery collector short distance recycling based on supercritical fluid as claimed in claim 9, special
Sign is, the first shut-off valve, the first decompression table, cooling are disposed on the connecting line of reaction kettle and carbon dioxide storage tank
Device, high-pressure pump, the second shut-off valve, the second decompression table.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810057140.0A CN108365287B (en) | 2018-01-22 | 2018-01-22 | Lithium battery negative electrode current collector short-range recovery method based on supercritical fluid |
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| CN201810057140.0A CN108365287B (en) | 2018-01-22 | 2018-01-22 | Lithium battery negative electrode current collector short-range recovery method based on supercritical fluid |
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| CN108365287A true CN108365287A (en) | 2018-08-03 |
| CN108365287B CN108365287B (en) | 2020-12-08 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114672019A (en) * | 2022-04-07 | 2022-06-28 | 江苏海洋大学 | In supercritical CO2Equipment and method for preparing polyaniline composite material under atmosphere |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1618142A (en) * | 2002-01-09 | 2005-05-18 | 史蒂文·E·斯鲁普 | System and method for removing an electrolyte from an energy storage and/or conversion device using a supercritical fluid |
| US20050244704A1 (en) * | 2002-01-09 | 2005-11-03 | Sloop Steven E | System and method for processing an end-of-life or reduced performance energy storage and/or conversion device using a supercritical fluid |
| CN102569941A (en) * | 2011-01-20 | 2012-07-11 | 常州翔宇资源再生科技有限公司 | Method for recycling negative electrode material of lithium ion battery by wet method |
| CN105406146A (en) * | 2015-12-31 | 2016-03-16 | 哈尔滨工业大学 | Carbon dioxide subcritical extraction, recycling and reusing method for electrolyte of waste lithium ion battery |
| CN105895984A (en) * | 2016-06-25 | 2016-08-24 | 芜湖格利特新能源科技有限公司 | Recycling process of lithium iron phosphate power battery |
| CN106688135A (en) * | 2014-08-06 | 2017-05-17 | 史蒂文·E·斯卢普 | Recycling positive-electrode material of a lithium-ion battery |
| CN107123839A (en) * | 2017-06-22 | 2017-09-01 | 宁波赛克雷特新能源科技有限公司 | Method for extracting and separating electrolyte components and active materials from battery |
-
2018
- 2018-01-22 CN CN201810057140.0A patent/CN108365287B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1618142A (en) * | 2002-01-09 | 2005-05-18 | 史蒂文·E·斯鲁普 | System and method for removing an electrolyte from an energy storage and/or conversion device using a supercritical fluid |
| US20050244704A1 (en) * | 2002-01-09 | 2005-11-03 | Sloop Steven E | System and method for processing an end-of-life or reduced performance energy storage and/or conversion device using a supercritical fluid |
| CN102569941A (en) * | 2011-01-20 | 2012-07-11 | 常州翔宇资源再生科技有限公司 | Method for recycling negative electrode material of lithium ion battery by wet method |
| CN106688135A (en) * | 2014-08-06 | 2017-05-17 | 史蒂文·E·斯卢普 | Recycling positive-electrode material of a lithium-ion battery |
| CN105406146A (en) * | 2015-12-31 | 2016-03-16 | 哈尔滨工业大学 | Carbon dioxide subcritical extraction, recycling and reusing method for electrolyte of waste lithium ion battery |
| CN105895984A (en) * | 2016-06-25 | 2016-08-24 | 芜湖格利特新能源科技有限公司 | Recycling process of lithium iron phosphate power battery |
| CN107123839A (en) * | 2017-06-22 | 2017-09-01 | 宁波赛克雷特新能源科技有限公司 | Method for extracting and separating electrolyte components and active materials from battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114672019A (en) * | 2022-04-07 | 2022-06-28 | 江苏海洋大学 | In supercritical CO2Equipment and method for preparing polyaniline composite material under atmosphere |
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| CN108365287B (en) | 2020-12-08 |
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