CN119706827B - A low-temperature homogeneous regeneration method for waste lithium-ion battery graphite - Google Patents
A low-temperature homogeneous regeneration method for waste lithium-ion battery graphiteInfo
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Abstract
本发明公开了一种废旧锂离子电池石墨低温均相再生方法，该方法是将磁性金属与废旧石墨球磨混合并压实后，置于惰性气氛下进行低温煅烧，得到初步修复石墨材料；所述初步修复石墨材料再次研磨并分散于溶液后经磁选去除磁性金属，即得再生石墨材料。本发明利用磁性金属与石墨紧密接触时可诱导石墨及近表面的缺陷位点低温修复，得到的再生石墨材料电化学性能好，且磁性金属可通过磁选去除，进一步提升了再生石墨材料的纯度。
The present invention discloses a low-temperature homogeneous regeneration method for waste lithium-ion battery graphite. The method comprises ball-milling and compacting a magnetic metal with waste graphite, followed by low-temperature calcination under an inert atmosphere to produce a pre-repaired graphite material. The pre-repaired graphite material is then ground again and dispersed in a solution, followed by magnetic separation to remove the magnetic metal, thereby producing a regenerated graphite material. This method utilizes the ability of the magnetic metal to induce low-temperature repair of defect sites in the graphite and near its surface when in close contact with the graphite. The resulting regenerated graphite material exhibits excellent electrochemical properties, and the magnetic metal can be removed by magnetic separation, further enhancing the purity of the regenerated graphite material.
Description
Technical Field
The invention relates to a graphite low-temperature homogeneous regeneration method for waste lithium ion batteries, and belongs to the technical field of waste battery recovery.
Background
Graphite belongs to strategic mineral resources in China, and plays a role of a pillar in national economy in China. Currently, graphite resources have been successfully used as lithium ion battery anode materials. With the rapid development of new energy industry, the lithium ion battery has been widely applied to various industries in China, but the limited service life of the lithium ion battery is first, and the lithium ion battery must be scrapped. The method is oriented to the tide of massive waste batteries, and the step of high-quality recovery of the waste batteries is achieved, so that the method is a key step for realizing the final loop of closed loop circulation of the new energy industry.
At present, the recovery of the graphite cathode of the lithium ion battery is divided into wet recovery and direct regeneration. The wet recovery is to extract key metal elements from the interior by acid-base reagents and the like, then stack the participated graphite waste, at present, most of the wet treated waste is used as fuel to burn and cause a great amount of waste of resources, and the direct regeneration is required to be calcined at 2800 ℃ for a long time and repair the graphite crystal phase. Although the direct regeneration means has high utilization efficiency of graphite resources, the problems of high energy consumption, large pollution and the like lead to lower economic value of graphite recovery, and most direct regeneration enterprises do not carry out the repair production work of waste graphite. In addition, waste graphite materials from different sources are damaged differently, and simple restoration cannot induce graphite homogenization restoration, so that the performance of the regenerated graphite is nonuniform, and finally the produced regenerated graphite enters a commercial market for circulation.
Chinese patent CN117954725A discloses a method for preparing high-value regenerated graphite by mixing waste lithium ion battery graphite negative electrode material with ammonium salt-strong alkali composite salt, calcining, washing and drying to obtain precursor material, mixing precursor material with low boiling point organic metal salt-energy storage type anion powder composite, and vacuum calcining. The method can effectively realize capacity restoration of the graphite cathode material, but the method can change the internal structure of the graphite material by alkali and high Wen Ke corrosion in the early stage, and the charge-discharge capacity performance restoration of the graphite electrode material depends on the mutual combination of the introduced metal ions and sulfur atoms or selenium atoms to form a high-capacity electrode material transition metal sulfur selenium compound, namely, partial irremovable magnetic substances are introduced during the restoration, which is also unfavorable for the commercial circulation of the graphite cathode material of the lithium battery.
Disclosure of Invention
Aiming at the problems of poor regeneration performance, high energy consumption, nonuniform performance and the like of the existing waste graphite, the invention aims to provide a low-temperature homogeneous regeneration method of waste lithium ion battery graphite. According to the method, the magnetic metal is introduced into the waste graphite, and through compaction treatment, the short-flow and low-energy-consumption regeneration of the waste graphite is realized by utilizing the fact that the magnetic metal can induce the graphite and near-surface defect sites to repair at low temperature when the magnetic metal is in close contact with the graphite, and the obtained regenerated graphite material has good multiplying power performance and high capacity.
In order to achieve the technical aim, the invention provides a low-temperature homogeneous regeneration method of graphite of a waste lithium ion battery, which comprises the steps of ball-milling, mixing and compacting magnetic metal and waste graphite, and then calcining at a low temperature in an inert atmosphere to obtain a primary repairing graphite material; and grinding the primary repairing graphite material again, dispersing the primary repairing graphite material in the solution, and removing the magnetic metal through magnetic separation to obtain the regenerated graphite material.
In the technical scheme of the invention, compaction treatment is a precondition of repair, and the introduction of magnetic metal is a key of repair. The invention is characterized in that firstly, the magnetic metal has a special electronic structure, free electrons in the magnetic metal can migrate to the defect site of graphite when the magnetic metal is in close contact with the graphite, thus filling the electron deficiency, stabilizing the structure of the graphite and promoting the repair of the defect, secondly, the magnetic metal can generate a local electric field near the surface of the graphite, and the local electric field is helpful for adjusting the arrangement of atoms and promoting the gradual healing of the defect for the defect caused by the processes of lithium ion deintercalation and the like, thirdly, the magnetic metal can play an effective catalytic role on the surface of the graphite, and can reduce the activation energy of reaction, thus realizing the repair at low temperature. The catalysis of the magnetic metal on the waste graphite depends on the contact degree between the waste graphite and the magnetic metal, and if no contact exists, the catalysis formed by the interface is difficult to complete. In addition, part of the graphite which is not contacted with the graphite cannot be repaired, so that the repairing effect is incomplete. According to the invention, the contact degree between the waste graphite and the magnetic substance can be remarkably improved through compaction treatment, the surface interface repairing effect of the waste graphite is improved, and finally the low-temperature homogeneous phase repairing of the waste graphite is realized. Compared with the prior art, the repaired graphite material can be removed through magnetic separation, and the purity of the regenerated graphite material is further improved without affecting the capacity and the performance of the repaired graphite material, so that the commercial application of the regenerated graphite material is realized.
The inventor discovers that compared with magnetic metal salt (magnetic metal ions), the magnetic separation method adopts magnetic metal, has larger particle size, is beneficial to magnetic separation at the rear end, and avoids the generation of waste acid and waste liquid. If the magnetic metal is changed into the corresponding metal salt, the metal salt can generate inhomogeneous metal simple substance particles due to decomposition and reduction in the calcining process, and partial particles with smaller dimensions can not be separated by magnetic separation and remain in the regenerated graphite material, and can only be subjected to acid washing, so that secondary damage can be generated to the regenerated graphite material by the acid washing. In addition, in the regeneration process caused by the traditional metal salt catalysis process, anions which are difficult to wash can be introduced, and organic carbon chains capable of decomposing amorphous carbon can be introduced into the organic metal salt, so that the yield of the material is reduced, and the electrochemical side reaction is aggravated. The large-size magnetic particles in the invention are beneficial to migration of carbon particles on the surface of graphite in a low-temperature environment, fill up the defects on the surface of the failed graphite particles, provide a pre-intercalation interlayer spacing for lithium ion storage and improve the capacity and rate capability of the material.
As a preferable scheme, the waste graphite is derived from waste lithium ion batteries, pole piece materials, lithium ion batteries without liquid injection and the like which are purchased in the market.
As a preferable scheme, the magnetic metal is at least one of cobalt, nickel and iron.
As a preferable scheme, the mass ratio of the magnetic metal to the waste graphite is (0.1-10): 1. The quality ratio of the magnetic metal to the waste graphite has direct influence on the repairing effect of the graphite, if the quality ratio is too low, the content of the magnetic metal is too low, enough active sites are difficult to provide for the waste graphite, the near surface of the waste graphite cannot be induced to realize uniform repairing at a low temperature, and if the quality ratio is too high, the content of the magnetic metal is too high, so that the treatment cost is increased, the heat energy is seriously utilized, the difficulty of removing the magnetic metal by subsequent magnetic separation is increased, and even the purity of the regenerated graphite material is reduced.
As a preferable mode, the magnetic metal is powder with D50 of 0.1-200 mu m. If the D50 of the magnetic metal is too small, the particle size is small, the activity of the metal powder is strong, the actions such as spontaneous combustion and the like are easy to occur in the air, the production and the preparation are unfavorable, and the magnetic metal is difficult to completely remove through the subsequent magnetic separation, while the magnetic metal D50 is too large, the particle size is large, and the magnetic metal is difficult to form close and uniform contact with the waste graphite, so that the near-surface homogeneous repair of the waste graphite is difficult to realize.
As a preferable scheme, the compacting pressure is 10-100 mpa. If the pressure is too small in the compacting process, close contact is difficult to form between the waste graphite and the magnetic metal, and the homogeneous repairing effect is reduced, and if the pressure is too large, particle breakage of the waste graphite occurs in the compacting process, the integral structure of the graphite is damaged, meanwhile, the mixed material after severe compacting is difficult to grind and disperse, and the magnetic metal is difficult to remove in the follow-up process.
As a preferable scheme, the low-temperature calcination atmosphere is one of argon, hydrogen and hydrogen-argon mixture.
As a preferable scheme, the low-temperature calcination condition is that the temperature is 500-1500 ℃ and the time is 1-20 h. If the calcination temperature is too low or the calcination time is too short, the magnetic metal activity and the carbon atom migration activity in the graphite are difficult to be completely excited, so that the defects and other problems are difficult to repair. And the calcining temperature is too high, the magnetic metal is melted and aggregated, and the induced repairing effect cannot be finished.
As a preferable scheme, the solution contains at least one dispersing agent of CMC (carboxymethyl cellulose), ethanol and sodium dodecyl benzene sulfonate, and the mass ratio of the dispersing agent to the primary repair graphite material is 1g (10-1 kg). According to the invention, through the tight connection between the compacted material and the graphite, if the agglomeration formed by partial magnetic metal and the graphite is difficult to dissociate only through simple crushing, partial magnetic particles possibly remain in the repaired graphite, so that the content of the magnetic substance in the repaired graphite is too high, and the commercial application standard is difficult to be met. Therefore, the graphite is dispersed in the aqueous phase solution, and the dissociation degree of the graphite material is improved. In addition, graphite has strong surface hydrophobicity, and is directly placed in aqueous solution, so that graphite materials are difficult to disperse in the aqueous solution. Therefore, the invention adds a proper amount of dispersing agent to promote the dispersion and dissociation of graphite particles in the water phase.
As a preferable scheme, the magnetic separation adopts a wet magnetic separator, the magnetic separation strength is 0.5T-2.0T, and the magnetic separation is circulated for 3-6 times. The removal effect of the magnetic metal introduced into the primary repair graphite material can be ensured within the selected magnetic separation intensity range, and the magnetic metal can be removed more thoroughly through multiple times of circulation, so that the quality of the regenerated graphite material is ensured.
As a preferred embodiment, the content of the magnetic metal powder in the regenerated graphite material is less than 50ppm.
The ball milling and other processes related by the invention are conventional operation processes in the prior art, and aim to convert the compacted and sintered mixed material into powder, so that the next dispersing and magnetic separation operation is facilitated.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) The method provided by the invention has the advantages of simple regeneration process, short flow, low energy consumption, simple operation, short period and high economic benefit.
2) According to the invention, the magnetic metal is introduced into the waste graphite and compacted, so that the graphite and near-surface defect sites can be induced to repair at low temperature when the magnetic metal is in close contact with the graphite, the obtained regenerated graphite material has good electrochemical performance, and the magnetic metal can be removed through magnetic separation, so that the purity of the regenerated graphite material is further improved.
3) The method can realize homogeneous regeneration of different types of waste graphite.
Drawings
FIG. 1 is a graph of electrochemical performance of three batches of graphite material repaired by example 5 of the present invention.
Fig. 2 is a graph of electrochemical performance of three batches of graphite material repaired by example 1 of the present invention.
As can be seen from a comparison of fig. 1 and fig. 2, the repair process of the present invention, in which the magnetic metal and compacting process are combined, has small batch-to-batch variation of the regenerated graphite material, and can realize homogeneous regeneration.
Detailed Description
The following examples are illustrative of the present invention and are not intended to limit the scope of the claims.
The waste graphite used in the invention is derived from waste batteries purchased in the market, and the waste lithium ion battery is subjected to safe discharge, manual disassembly, negative pressure drying and other processes to obtain a relatively pure negative electrode plate of the waste lithium ion battery, and then subjected to ultrasonic multiple water washing, drying and other processes to obtain the waste lithium ion battery graphite material.
The content of the magnetic metal powder in the regenerated graphite material obtained by the treatment process of the magnetic metal, the compaction treatment and the magnetic separation is less than 50ppm.
In the embodiment of the invention, the volume ratio of the dispersing agent to water in the aqueous solution containing the dispersing agent is 1:1, and the mass ratio of the dispersing agent to the primary repair graphite material is 0.001g:1g.
Example 1 (control)
1G of waste graphite powder is placed under a press for compaction, and the pressure is selected to be 20MPa. And (3) placing the pressed material into a tube furnace, calcining at 800 ℃ for 10 hours under the nitrogen atmosphere, and naturally cooling to obtain the regenerated graphite material.
Example 2 (control)
Weighing magnetic metal powder (D50, 10 mu m) and waste graphite according to a mass ratio of 2:1 (cobalt is 2g, graphite is 1 g), then placing the materials into a ball mill for ball milling and mixing, calcining the mixed materials at 800 ℃ for 10 hours in a nitrogen atmosphere, and then naturally cooling. The cooled material was again put into a ball mill to be ground, and the ground material was dispersed in an aqueous solution containing ethanol. And (3) carrying out magnetic separation by using a wet magnetic separator, wherein the magnetic separation strength is 1.0T, the magnetic separation times are 5 times, and drying the magnetic-separated material to obtain the regenerated graphite material.
Example 3 (control)
The magnetic metal powder (D50, 10 μm) and the waste graphite were weighed according to a mass ratio of 2:1 (cobalt is 2g, graphite is 1 g), then put into a ball mill for ball milling and mixing, and the mixed powder was compacted under a press machine with a pressure of 20MPa. And placing the pressed material into a tube furnace, calcining at 800 ℃ for 10 hours under the nitrogen atmosphere, and then naturally cooling. And (3) grinding the cooled material in a ball mill again, and carrying out magnetic separation on the ground material by using a dry magnetic separator, wherein the magnetic separation strength is 1.0T, the magnetic separation times are 5 times, and the material after magnetic separation is dried to obtain the regenerated graphite material.
Example 4 (control)
The magnetic metal powder (D50, 10 μm) and the waste graphite were weighed according to a mass ratio of 2:1 (cobalt is 2g, graphite is 1 g), then put into a ball mill for ball milling and mixing, and the mixed powder was compacted under a press machine with a pressure of 20MPa. And (3) carrying out magnetic separation by using a wet magnetic separator (the dispersing agent is ethanol water solution), wherein the magnetic separation strength is 1.0T, the magnetic separation times are 5 times, and drying the magnetic-separated material to obtain the regenerated graphite material.
Example 5
The magnetic metal powder (D50, 10 μm) and the waste graphite were weighed according to a mass ratio of 2:1 (cobalt is 2g, graphite is 1 g), then put into a ball mill for ball milling and mixing, and the mixed powder was compacted under a press machine with a pressure of 20MPa. And placing the pressed material into a tube furnace, calcining at 800 ℃ for 10 hours under the nitrogen atmosphere, and then naturally cooling. The cooled material was again put into a ball mill to be ground, and the ground material was dispersed in an aqueous solution containing ethanol. And (3) carrying out magnetic separation by using a wet magnetic separator, wherein the magnetic separation strength is 1.0T, the magnetic separation times are 5 times, and drying the magnetic-separated material to obtain the regenerated graphite material.
Example 6
The magnetic metal powder (D50, 10 μm) and the waste graphite were weighed according to a mass ratio of 2:1 (nickel is 2g, graphite is 1 g), then put into a ball mill for ball milling and mixing, and the mixed powder was compacted under a press machine with a pressure of 20MPa. And placing the pressed material into a tube furnace, calcining at 800 ℃ for 10 hours under the nitrogen atmosphere, and then naturally cooling. The cooled material was again put into a ball mill to be ground, and the ground material was dispersed in an aqueous solution containing ethanol. And (3) carrying out magnetic separation by using a wet magnetic separator, wherein the magnetic separation strength is 1.0T, the magnetic separation times are 5 times, and drying the magnetic-separated material to obtain the regenerated graphite material.
Example 7
The magnetic metal powder (D50, 0.1 μm) and the waste graphite were weighed according to a mass ratio of 2:1 (cobalt is 2g, graphite is1 g), then put into a ball mill for ball milling and mixing, and the mixed powder was compacted under a press machine with a pressure of 20MPa. And placing the pressed material into a tube furnace, calcining at 800 ℃ for 10 hours under the nitrogen atmosphere, and then naturally cooling. The cooled material was again put into a ball mill to be ground, and the ground material was dispersed in an aqueous solution containing ethanol. And (3) carrying out magnetic separation by using a wet magnetic separator, wherein the magnetic separation strength is 1.0T, the magnetic separation times are 5 times, and drying the magnetic-separated material to obtain the regenerated graphite material.
Example 8
The magnetic metal powder (D50, 200 μm) and the waste graphite were weighed according to a mass ratio of 2:1 (cobalt is 2g, graphite is1 g), then put into a ball mill for ball milling and mixing, and the mixed powder was compacted under a press machine with a pressure of 20MPa. And placing the pressed material into a tube furnace, calcining at 800 ℃ for 10 hours under the nitrogen atmosphere, and then naturally cooling. The cooled material was again put into a ball mill to be ground, and the ground material was dispersed in an aqueous solution containing ethanol. And (3) carrying out magnetic separation by using a wet magnetic separator, wherein the magnetic separation strength is 1.0T, the magnetic separation times are 5 times, and drying the magnetic-separated material to obtain the regenerated graphite material.
Example 9
The magnetic metal powder (D50, 10 μm) and the waste graphite are weighed according to the mass ratio of 0.1:1 (cobalt is 0.1g, graphite is 1 g), then the mixture is put into a ball mill for ball milling and mixing, and the mixed powder is compacted under a press machine, wherein the pressure is selected to be 20MPa. And placing the pressed material into a tube furnace, calcining at 800 ℃ for 10 hours under the nitrogen atmosphere, and then naturally cooling. The cooled material was again put into a ball mill to be ground, and the ground material was dispersed in an aqueous solution containing ethanol. And (3) carrying out magnetic separation by using a wet magnetic separator, wherein the magnetic separation strength is 1.0T, the magnetic separation times are 5 times, and drying the magnetic-separated material to obtain the regenerated graphite material.
Example 10
The magnetic metal powder (D50, 10 μm) and the waste graphite were weighed according to a mass ratio of 10:1 (cobalt is 10g, graphite is 1 g), then put into a ball mill for ball milling and mixing, and the mixed powder was compacted under a press machine with a pressure of 20MPa. And placing the pressed material into a tube furnace, calcining at 800 ℃ for 10 hours under the nitrogen atmosphere, and then naturally cooling. The cooled material was again put into a ball mill to be ground, and the ground material was dispersed in an aqueous solution containing ethanol. And (3) carrying out magnetic separation by using a wet magnetic separator, wherein the magnetic separation strength is 1.0T, the magnetic separation times are 5 times, and drying the magnetic-separated material to obtain the regenerated graphite material.
Example 11
The magnetic metal powder (D50, 10 μm) and the waste graphite were weighed according to a mass ratio of 2:1 (cobalt is 2g, graphite is 1 g), then put into a ball mill for ball milling and mixing, and the mixed powder was compacted under a press machine with a pressure of 10MPa. And placing the pressed material into a tube furnace, calcining at 800 ℃ for 10 hours under the nitrogen atmosphere, and then naturally cooling. The cooled material was again put into a ball mill to be ground, and the ground material was dispersed in an aqueous solution containing ethanol. And (3) carrying out magnetic separation by using a wet magnetic separator, wherein the magnetic separation strength is 1.0T, the magnetic separation times are 5 times, and drying the magnetic-separated material to obtain the regenerated graphite material.
Example 12
The magnetic metal powder (D50, 10 μm) and the waste graphite were weighed according to a mass ratio of 2:1 (cobalt is 2g, graphite is 1 g), then put into a ball mill for ball milling and mixing, and the mixed powder was compacted under a press machine with a pressure of 100MPa. And placing the pressed material into a tube furnace, calcining at 800 ℃ for 10 hours under the nitrogen atmosphere, and then naturally cooling. The cooled material was again put into a ball mill to be ground, and the ground material was dispersed in an aqueous solution containing ethanol. And (3) carrying out magnetic separation by using a wet magnetic separator, wherein the magnetic separation strength is 1.0T, the magnetic separation times are 5 times, and drying the magnetic-separated material to obtain the regenerated graphite material.
Example 13
The magnetic metal powder (D50, 10 μm) and the waste graphite were weighed according to a mass ratio of 2:1 (cobalt is 2g, graphite is 1 g), then put into a ball mill for ball milling and mixing, and the mixed powder was compacted under a press machine with a pressure of 20MPa. And placing the pressed material into a tube furnace, calcining at 800 ℃ for 10 hours under the argon atmosphere, and then naturally cooling. The cooled material was again put into a ball mill to be ground, and the ground material was dispersed in an aqueous solution containing ethanol. And (3) carrying out magnetic separation by using a wet magnetic separator, wherein the magnetic separation strength is 1.0T, the magnetic separation times are 5 times, and drying the magnetic-separated material to obtain the regenerated graphite material.
Example 14
The magnetic metal powder (D50, 10 μm) and the waste graphite were weighed according to a mass ratio of 2:1 (cobalt is 2g, graphite is 1 g), then put into a ball mill for ball milling and mixing, and the mixed powder was compacted under a press machine with a pressure of 20MPa. And placing the pressed material into a tube furnace, calcining at 500 ℃ for 10 hours under the nitrogen atmosphere, and then naturally cooling. The cooled material was again put into a ball mill to be ground, and the ground material was dispersed in an aqueous solution containing ethanol. And (3) carrying out magnetic separation by using a wet magnetic separator, wherein the magnetic separation strength is 1.0T, the magnetic separation times are 5 times, and drying the magnetic-separated material to obtain the regenerated graphite material.
Example 15
The magnetic metal powder (D50, 10 μm) and the waste graphite were weighed according to a mass ratio of 2:1 (cobalt is 2g, graphite is 1 g), then put into a ball mill for ball milling and mixing, and the mixed powder was compacted under a press machine with a pressure of 20MPa. Placing the pressed material into a tube furnace, calcining at 1500 ℃ for 10 hours under the nitrogen atmosphere, and then naturally cooling. The cooled material was again put into a ball mill to be ground, and the ground material was dispersed in an aqueous solution containing ethanol. And (3) carrying out magnetic separation by using a wet magnetic separator, wherein the magnetic separation strength is 1.0T, the magnetic separation times are 5 times, and drying the magnetic-separated material to obtain the regenerated graphite material.
Example 16
The magnetic metal powder (D50, 10 μm) and the waste graphite were weighed according to a mass ratio of 2:1 (cobalt is 2g, graphite is 1 g), then put into a ball mill for ball milling and mixing, and the mixed powder was compacted under a press machine with a pressure of 20MPa. And placing the pressed material into a tube furnace, calcining at 800 ℃ for 1h under the nitrogen atmosphere, and then naturally cooling. The cooled material was again put into a ball mill to be ground, and the ground material was dispersed in an aqueous solution containing ethanol. And (3) carrying out magnetic separation by using a wet magnetic separator, wherein the magnetic separation strength is 1.0T, the magnetic separation times are 5 times, and drying the magnetic-separated material to obtain the regenerated graphite material.
Example 17
The magnetic metal powder (D50, 10 μm) and the waste graphite were weighed according to a mass ratio of 2:1 (cobalt is 2g, graphite is 1 g), then put into a ball mill for ball milling and mixing, and the mixed powder was compacted under a press machine with a pressure of 20MPa. And placing the pressed material into a tube furnace, calcining at 800 ℃ for 20 hours under the nitrogen atmosphere, and then naturally cooling. The cooled material was again put into a ball mill to be ground, and the ground material was dispersed in an aqueous solution containing ethanol. And (3) carrying out magnetic separation by using a wet magnetic separator, wherein the magnetic separation strength is 1.0T, the magnetic separation times are 5 times, and drying the magnetic-separated material to obtain the regenerated graphite material.
Example 18
The magnetic metal powder (D50, 10 μm) and the waste graphite were weighed according to a mass ratio of 2:1 (cobalt is 2g, graphite is 1 g), then put into a ball mill for ball milling and mixing, and the mixed powder was compacted under a press machine with a pressure of 20MPa. And placing the pressed material into a tube furnace, calcining at 800 ℃ for 10 hours under the nitrogen atmosphere, and then naturally cooling. The cooled material was again put into a ball mill to be ground, and the ground material was dispersed in an aqueous solution containing CMC. And (3) carrying out magnetic separation by using a wet magnetic separator, wherein the magnetic separation strength is 1.0T, the magnetic separation times are 5 times, and drying the magnetic-separated material to obtain the regenerated graphite material.
Example 19
The magnetic metal powder (D50, 10 μm) and the waste graphite were weighed according to a mass ratio of 2:1 (cobalt is 2g, graphite is 1 g), then put into a ball mill for ball milling and mixing, and the mixed powder was compacted under a press machine with a pressure of 20MPa. And placing the pressed material into a tube furnace, calcining at 800 ℃ for 10 hours under the nitrogen atmosphere, and then naturally cooling. The cooled material was again put into a ball mill to be ground, and the ground material was dispersed in an aqueous solution containing ethanol. And (3) carrying out magnetic separation by using a wet magnetic separator, wherein the magnetic separation strength is 0.5T, the magnetic separation times are 5 times, and drying the magnetic-separated material to obtain the regenerated graphite material.
Example 20
The magnetic metal powder (D50, 10 μm) and the waste graphite were weighed according to a mass ratio of 2:1 (cobalt is 2g, graphite is 1 g), then put into a ball mill for ball milling and mixing, and the mixed powder was compacted under a press machine with a pressure of 20MPa. And placing the pressed material into a tube furnace, calcining at 800 ℃ for 10 hours under the nitrogen atmosphere, and then naturally cooling. The cooled material was again put into a ball mill to be ground, and the ground material was dispersed in an aqueous solution containing ethanol. And (3) carrying out magnetic separation by using a wet magnetic separator, wherein the magnetic separation strength is 2.0T, the magnetic separation times are 5 times, and drying the magnetic-separated material to obtain the regenerated graphite material.
Example 21
The magnetic metal powder (D50, 10 μm) and the waste graphite were weighed according to a mass ratio of 2:1 (cobalt is 2g, graphite is 1 g), then put into a ball mill for ball milling and mixing, and the mixed powder was compacted under a press machine with a pressure of 20MPa. And placing the pressed material into a tube furnace, calcining at 800 ℃ for 10 hours under the nitrogen atmosphere, and then naturally cooling. The cooled material was again put into a ball mill to be ground, and the ground material was dispersed in an aqueous solution containing ethanol. And (3) carrying out magnetic separation by using a wet magnetic separator, wherein the magnetic separation strength is 1.0T, the magnetic separation times are 3 times, and drying the magnetic-separated material to obtain the regenerated graphite material.
Example 22
The magnetic metal powder (D50, 10 μm) and the waste graphite were weighed according to a mass ratio of 2:1 (cobalt is 2g, graphite is 1 g), then put into a ball mill for ball milling and mixing, and the mixed powder was compacted under a press machine with a pressure of 20MPa. And placing the pressed material into a tube furnace, calcining at 800 ℃ for 10 hours under the nitrogen atmosphere, and then naturally cooling. The cooled material was again put into a ball mill to be ground, and the ground material was dispersed in an aqueous solution containing ethanol. And (3) carrying out magnetic separation by using a wet magnetic separator, wherein the magnetic separation strength is 1.0T, the magnetic separation times are 6 times, and drying the magnetic-separated material to obtain the regenerated graphite material.
The regenerated graphite materials of examples 1 to 22 were tested as follows, and the results are shown in Table 1.
1) Preparation of samples
In each example, waste graphite is derived from waste batteries purchased in the market, three materials of regenerated materials, acetylene black and sodium carboxymethylcellulose (CMC) are added according to the mass ratio of 8/1/1, quantitative deionized water is added to prepare uniform slurry, the obtained slurry is coated on copper foil, then the copper foil is put into a vacuum oven for drying at 100 ℃ for 24 hours, the obtained pole piece is cut by a slicing machine, and is sheared into small wafers with the diameter of 1cm, so that the obtained anode electrode material is obtained, wherein more than 1mg of active substances are loaded on the copper foil.
And placing the obtained positive electrode plate, electrolyte, lithium plate, battery shell, diaphragm and the like in an argon glove box for battery assembly. After sealing, the obtained battery is an assembled button battery.
Note that all examples were prepared using the above electrode materials.
2) Test method
And standing the obtained button cell for 12 hours, and then placing the button cell on a blue electric test channel for electrochemical performance test, wherein the current density is set to be 1.0C, and the voltage interval is set to be 0.01-2.5V. The obtained data is the data directly displayed on the blue electric tester, and the data is directly taken.
Table 1 results of electrochemical performance measurements in the examples
Claims (6)
Priority Applications (1)
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| CN202411885139.9A CN119706827B (en) | 2024-12-20 | 2024-12-20 | A low-temperature homogeneous regeneration method for waste lithium-ion battery graphite |
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