CN108365287B - Lithium battery negative electrode current collector short-range recovery method based on supercritical fluid - Google Patents

Lithium battery negative electrode current collector short-range recovery method based on supercritical fluid Download PDF

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CN108365287B
CN108365287B CN201810057140.0A CN201810057140A CN108365287B CN 108365287 B CN108365287 B CN 108365287B CN 201810057140 A CN201810057140 A CN 201810057140A CN 108365287 B CN108365287 B CN 108365287B
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negative electrode
lithium battery
supercritical fluid
current collector
recovery method
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CN108365287A (en
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刘维桥
邹超
刘欢
刘玉
潘君丽
周全法
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Jiangsu University of Technology
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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
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    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract

A short-range recovery method of a lithium battery negative current collector based on supercritical fluid comprises the steps of putting a lithium battery negative material into a reaction kettle, adding a solvent to completely immerse the lithium battery negative material, using the supercritical fluid to dissolve and strip organic components in the negative material at a certain temperature and under a certain pressure under the assistance of mechanical stirring, and separating a copper foil current collector from conductive carbon black so as to recover the copper foil current collector. According to the invention, the negative current collector is stripped without using an organic solvent and alkali liquor, and the total removal rate of other substances such as the electric carbon black and other negative materials is 94.68%; the treatment efficiency is high, the cost is low, secondary pollution can not be generated in the treatment process, and the treatment process is green and environment-friendly.

Description

Lithium battery negative electrode current collector short-range recovery method based on supercritical fluid
Technical Field
The invention belongs to the technical field of waste battery recovery, and particularly relates to a short-range recovery method of a lithium battery negative current collector based on supercritical fluid.
Background
Since the 90 s of the last century since the commercialization of lithium ion batteries, lithium ion batteries have been replacing various other secondary batteries due to their advantages of high voltage, high energy density, long cycle life, good safety, no memory effect, etc. The negative electrode material of the lithium battery is prepared by uniformly mixing 90% of conductive carbon black, 5% of acetylene black and 5% of a binder, and coating the mixture on a copper foil current collector.
The existing recovery method of the current collector of the negative electrode of the lithium battery generally adopts a water washing method or a high-temperature method for treatment, separates the current collector from other materials such as conductive carbon black and the like, and then directly recovers the current collector. For example, chinese patent publication No. CN102569941 proposes a method for wet recovery of lithium ion battery materials, in which carbon-coated copper foil is placed in a temperature-controlled washing tank with a stirring device, and the temperature of the water is continuously maintained between 70 ℃ and 100 ℃ and stirred. Although the process is simple, the method can not completely wash off the carbon powder. Further, as disclosed in chinese patent publication No. CN105552468, a method for treating a negative electrode material of a lithium battery by a high temperature method is proposed, in which the negative electrode material subjected to the immersion pretreatment is calcined at a high temperature of 300 to 500 ℃ for 4 hours in an air atmosphere, so that a negative active material is separated from a copper foil. This high temperature treatment process is energy intensive and generates waste gases during the treatment process.
Therefore, it is necessary to provide a recovery method which is simple in process, low in cost, environmentally friendly, and capable of ensuring a high recovery rate of the negative electrode current collector.
Disclosure of Invention
In order to overcome the defect that the short-range recovery process of the lithium battery negative current collector is not environment-friendly in the prior art, the invention provides a short-range recovery method and a reactor of the lithium battery negative current collector based on a supercritical fluid.
A lithium battery negative current collector short-range recovery method based on supercritical fluid has the innovation points that: according to the method, the supercritical fluid is adopted to dissolve organic components in the lithium battery negative electrode material at a certain temperature and pressure, so that the purpose of stripping the negative electrode current collector is achieved.
Further, the method specifically comprises the steps of after the lithium battery is fully discharged, manually disassembling the battery, sorting out the negative electrode material, and crushing the negative electrode material to 4-10 cm2After the size is increased, the lithium battery anode material is placed into a reaction kettle, a solvent is added to completely immerse the lithium battery anode material, mechanical stirring is assisted, then supercritical fluid is pumped into the reaction kettle through a high-pressure pump, a binder in the nickel-cobalt-manganese ternary lithium battery anode material is dissolved under certain temperature and pressure conditions, an anode current collector is peeled off, the peeled anode current collector can be directly recycled, and anode active substances can be further recycled after being leached.
Furthermore, the negative electrode material of the lithium battery is at least one of a cobalt acid lithium battery, a lithium manganate battery, a lithium iron phosphate battery, a nickel-cobalt-manganese ternary lithium battery and a nickel-cobalt-aluminum ternary lithium battery.
Further, the mechanical stirring speed is 10-500 rpm, and the solid-to-liquid ratio of the negative electrode material to water is 0.1% -10%; preferably, the stirring speed is 300-400 rpm, and the solid-to-liquid ratio of the negative electrode material to water is 2% -5%.
Further, the temperature in the stripping process is 40-90 ℃, and the stripping pressure is 8-16 MPa; preferably, the temperature in the stripping process is 50-70 ℃, and the stripping pressure is 10-12 MPa.
Further, the stripping time is 10-300 min; preferably, the stripping time is 20-60 min.
Further, the supercritical fluid is carbon dioxide, and the solvent is any one of water, ethanol or acetone.
The utility model provides a reactor that lithium cell negative pole mass flow body short distance was retrieved based on supercritical fluid, includes through tube coupling reation kettle and carbon dioxide storage tank the reation kettle is provided with the heating jacket outward, is provided with the agitator in the reation kettle.
And a first stop valve, a first decompression meter, a cooler, a high-pressure pump, a second stop valve and a second decompression meter are sequentially arranged on a connecting pipeline of the reaction kettle and the carbon dioxide storage tank.
The invention provides a method for short-range recovery of a lithium battery cathode current collector by using supercritical fluid, which has the following advantages compared with the prior art:
according to the invention, the negative current collector is stripped without using an organic solvent and alkali liquor, and the copper foil current collector and the conductive carbon black are separated at a certain temperature and pressure by adopting a supercritical fluid, so that the copper foil current collector is recovered, and the total removal rate of other substances of negative materials such as the conductive carbon black is 94.68%; the treatment efficiency is high, the cost is low, secondary pollution can not be generated in the treatment process, and the treatment process is green and environment-friendly.
Drawings
FIG. 1: the supercritical fluid processing system structure schematic diagram of the method for short-range recovery of the lithium battery cathode current collector by the supercritical fluid is disclosed. In the figure: 1. a carbon dioxide storage tank; 2. a first shut-off valve; 3. a first decompression table; 4. a cooler; 5. a high pressure pump; 6. a second stop valve; 7. a second decompression table; 8. a stirrer; 9. a third stop valve; 10. a reaction kettle; 11. and (4) heating the sleeve.
Detailed Description
A reactor for short-range recovery of a lithium battery negative current collector based on supercritical fluid comprises a reaction kettle 10, a carbon dioxide storage tank 1 and a heating sleeve 11, wherein the reaction kettle 10 is connected through a pipeline, the heating sleeve 11 is arranged outside the reaction kettle 10, and a stirrer 8 is arranged in the reaction kettle 10. A first stop valve 2, a first decompression meter 3, a cooler 4, a high-pressure pump 5, a second stop valve 6 and a second decompression meter 7 are sequentially arranged on a connecting pipeline of the reaction kettle 10 and the carbon dioxide storage tank 1, and a third stop valve 9 is arranged outside the reaction kettle 10.
Example 1
After the cobalt acid lithium battery is fully discharged, the battery is manually disassembled, the cathode material is sorted out and crushed to 4cm2After the size is increased, the mixture is placed into a reaction kettle of a reactor, a proper amount of water is added according to the solid-liquid ratio of 2%, the mechanical stirring speed is controlled to be 300rpm, then the supercritical fluid is pumped into the reaction kettle through a high-pressure pump, the temperature in the stripping process is controlled to be 50 ℃, the stripping pressure is 10MPa, the stripping time is 20min, organic components in the negative electrode material are dissolved, and the negative electrode current collector is stripped. The total removal rate of other substances of the negative electrode material such as conductive carbon black was 99.42%.
Example 2
After the lithium iron phosphate battery is fully discharged, manually disassembling the battery, sorting out a negative electrode material, and crushing the negative electrode material to 7cm2After the size is increased, the mixture is placed into a reaction kettle of a reactor, a proper amount of ethanol is added according to the solid-liquid ratio of 4%, the mechanical stirring speed is controlled to be 400rpm, then the supercritical fluid is pumped into the reaction kettle through a high-pressure pump, the temperature in the stripping process is controlled to be 60 ℃, the stripping pressure is controlled to be 11MPa, the stripping time is 40min, organic components in the negative electrode material are dissolved, and the negative electrode current collector is stripped. The total removal rate of other substances of the negative electrode material such as conductive carbon black was 98.73%.
Example 3
After the nickel-cobalt-manganese ternary lithium battery is fully discharged, the battery is manually disassembled, the negative electrode material is sorted out and crushed to 10cm2After the size is increased, the mixture is placed into a reaction kettle of a reactor, a proper amount of water is added according to the solid-liquid ratio of 5%, the mechanical stirring speed is controlled to be 500rpm, then the supercritical fluid is pumped into the reaction kettle through a high-pressure pump, the temperature in the stripping process is controlled to be 60 ℃, the stripping pressure is 12MPa, the stripping time is 90min, organic components in the negative electrode material are dissolved, and the negative electrode current collector is stripped. Of other negative electrode materials, e.g. electrical blackThe total removal was 99.10%.
Example 4
After the lithium manganate battery is fully discharged, the battery is manually disassembled, the cathode material is sorted out and crushed to 1cm2After the size is increased, the mixture is placed into a reaction kettle of a reactor, a proper amount of water is added according to the solid-liquid ratio of 10%, the mechanical stirring speed is controlled to be 10rpm, then the supercritical fluid is pumped into the reaction kettle through a high-pressure pump, the temperature in the stripping process is controlled to be 40 ℃, the stripping pressure is 8MPa, the stripping time is 300min, organic components in the negative electrode material are dissolved, and the negative electrode current collector is stripped. The total removal rate of other substances of the negative electrode material such as the electrical carbon black is 90.25%.
Example 5
After the nickel-cobalt-manganese ternary lithium battery and the nickel-cobalt-aluminum ternary lithium battery are fully discharged in a mixing mode according to the ratio of 1:1, the batteries are manually disassembled, the negative electrode materials are sorted out, the batteries are mixed according to the ratio of 1:1 and crushed to 5cm2After the size is increased, the mixture is placed into a reaction kettle of a reactor, a proper amount of water is added according to the solid-liquid ratio of 0.1%, the mechanical stirring speed is controlled to be 420rpm, then the supercritical fluid is pumped into the reaction kettle through a high-pressure pump, the temperature in the stripping process is controlled to be 90 ℃, the stripping pressure is controlled to be 12MPa, the stripping time is 20min, organic components in the battery negative electrode material are dissolved, and the negative electrode current collector is stripped. The total removal rate of other substances of the negative electrode material such as the electrical carbon black is 94.68%.
The following table shows the process parameters and the corresponding post-strip rate results for examples 1-5
Figure BDA0001554104260000051
Figure BDA0001554104260000061
The method has the advantages of good stripping effect, simple process and low cost, the stripping rate of the negative current collector is over 90 percent, and the treatment does not generate secondary pollution, thereby being an environment-friendly green treatment process.

Claims (7)

1. A short-range recovery method of a lithium battery negative current collector based on a supercritical fluid is characterized by comprising the steps of putting a lithium battery negative material into a reaction kettle, adding a solvent to completely immerse the lithium battery negative material, mechanically stirring for assistance, and dissolving and stripping organic components in the negative material by using the supercritical fluid under the conditions that the temperature is 40-90 ℃ and the pressure is 8-16 MPa; the supercritical fluid is carbon dioxide, and the solvent is water.
2. The short-distance recovery method of the lithium battery negative electrode current collector based on the supercritical fluid as claimed in claim 1, wherein the lithium battery negative electrode material is obtained by fully discharging the lithium battery, manually disassembling the battery, sorting the negative electrode material, and crushing the negative electrode material to 4-10 cm2Size; and pumping the supercritical fluid into a reaction kettle through a high-pressure pump.
3. The short-distance recovery method for the negative electrode current collector of the lithium battery based on the supercritical fluid as claimed in claim 1 or 2, wherein the negative electrode material of the lithium battery is at least one of a lithium cobalt oxide battery, a lithium manganate battery, a lithium iron phosphate battery, a nickel cobalt manganese ternary lithium battery and a nickel cobalt aluminum ternary lithium battery.
4. The short-distance recovery method of the negative electrode current collector of the lithium battery based on the supercritical fluid as claimed in claim 1, wherein the speed of mechanical stirring is 10-500 rpm, and the solid-to-liquid ratio of the negative electrode material to water is 0.1% -10%.
5. The short-distance recovery method for the negative electrode current collector of the lithium battery based on the supercritical fluid as claimed in claim 4, wherein the speed of mechanical stirring is 300-400 rpm, and the solid-to-liquid ratio of the negative electrode material to water is 2% -5%.
6. The short-distance recovery method for the negative electrode current collector of the lithium battery based on the supercritical fluid as claimed in claim 1, wherein the stripping time for stripping the negative electrode material by the supercritical fluid dissolution is 10-300 min.
7. The short-distance recovery method for the negative electrode current collector of the lithium battery based on the supercritical fluid as claimed in claim 6, wherein the temperature for dissolving and stripping the negative electrode material by the supercritical fluid is 50-70 ℃, the pressure is 10-12 MPa, and the stripping time is 20-60 min.
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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
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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
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
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

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